Rovers were left to rue missed opportunities as they went down to a 2-1 loss to Chelsea at Ewood Park.
A bright opening saw the home side create a hatful of chances before finally taking the lead on 22 minutes when Benjani scored his first in Rovers colours, powerfully heading home El-Hadji Diouf's centre.
Though against the run of play Chelsea levelled just before the break, Nicolas Anelka applying the finishing touch after Didier Drogba's knockdown.
The second half was a more even affair, Robinson denying Zhirkov, whilst Mame Biram Diouf couldn't latch onto Pedersen's low free-kick.
But it was the missed chance from Jason Roberts when through on goal that Rovers would regret, Branislav Ivanovic punishing Rovers with a back post header just a minute later.
It was harsh on Rovers as they certainly deserved something from the match, but once again were left regretting what might have been.
Sam Allardyce had made four changes from the side that faced Liverpool at Anfield six days earlier.
The Rovers boss welcomed back defensive duo Christopher Samba and Ryan Nelsen, Mame Biram Diouf returned to the starting eleven whilst there was a first start in Rovers colours for striker Benjani.
Steven Nzonzi missed out due the hamstring strain picked up last week, Martin Olsson, David Dunn and Niko Kalinic dropped to the bench.
A minutes applause preceded the game to mark the sad passing of Ronnie Clayton, both managers joining Chairman John Williams alongside Ronnie's two sons on the touchline.
Rovers started the game brightly, matching their 4-3-3 formation, taking the game to the champions, the movement of Rovers' front three of El-Hadji Diouf, Benjani and Mame Biram Diouf backed up by the willing runners of Emerton and Pedersen.
On eleven a typical run from Emerton saw him burst through in on goal, he looked to switch the ball to his left to Benjani but Alex blocked effectively with a boot.
Chelsea were then thankful to their captain John Terry for keeping the scores level, first he headed a dangerous cross from El-Hadji Diouf away from the threatening Mame Biram Diouf, on the follow-up Morten Gamst Pedersen volleyed goalwards but Terry was there to block the effort.
Moments later Mame Diouf latched onto a forward ball from Emerton but Terry deflected the shot wide.
It was all one way traffic towards Petr Cech's goal and the giant stopper pulled off a stupendous save on 16 minutes. Mame Biram Diouf spotted the opportunity for a chip, and as Cech slipped in the six yard box the ball seemed destined to go into the back of the net until the Chelsea 'keeper somehow thrust a hand up to claw the ball wide.
Chance followed chance, Emerton onto Benjani but he shot at Cech, the rebound came to the Zimbabwean but his header lacked the power to trouble the visitors.
The deadlock was finally broken at the midway point of the half. Initially a corner from the left was cleared, Pedersen headed back to El-Hadji Diouf who swung over a teasing cross for Benjani to mark his first Rovers start with his first Rovers goal as he rose highest in the area to powerfully head home.
It was no more than Rovers deserved.
Rovers continued to look the brighter side, a quick break involving Mame Biram Diouf and Brett Emerton saw the Australian switch the ball inside to El-Hadji Diouf, Cech palmed away his back post destined cross, Emerton unable to force the ball home.
Aside from an early cross that eluded Didier Drogba, Chelsea had been strangely off colour but that was to change as the half drew to a close.
Michael Essien served notice on 38 minutes when he deftly flicked a shot from the edge of the area narrowly wide. The Ghanian requiring very little backlift on the shot.
Sixty seconds later and Chelsea were level. Their front three had been eerie quiet, but all combined as Florent Malouda crossed to Drogba at the back post and he nodded down for Nicolas Anelka to sweep home.
Rovers ended the half as they started, on the attack, but Martin Olsson's deep cross couldn't be reached by the lively Benjani.
Having lost Gael Givet on 35 minutes through injury, Rovers then reappeared in the second half without their first half talisman Benjani. Jason Roberts, back from injury, making his first appearance of the season.
The visitors started the second half the better of the two sides, Ashely Cole collecting an Essien pass on the edge of the area but the England man, with time to shoot, put his effort well wide.
Yuri Zhirkov tested Paul Robinson with a dipping strike, the Rovers goalkeeper standing up well to push the Russian's shot wide.
But it should have been Rovers celebrating a second goal on 62 minutes as Pedersen's low freekick was flicked on by Jason Roberts but Mame Biram Diouf couldn't convert at the back post.
Carlo Ancelotti sent on Daniel Sturridge for the ineffective Florent Malouda and almost having an immediate impact, sending a vicious 20 yard strike inches wide of the post.
Rovers sent on David Dunn for El-Hadji Diouf for the final ten minutes and like Sturridge before him, he too impressed immediately. This time it was with a cross into the box, standing the ball up well at the back post but Mame Biram Diouf couldn't direct his header past Cech.
Diouf himself then turned provider for what would prove to be Rovers' pivotal chance. The Senegal striker sending the ball over from the right for Jason Roberts who burst inside Ivanovic, but whilst his shot beat Cech, the ball crept the wrong side of the post.
Rovers were left to rue that miss in the worst possible way as sixty seconds later Chelsea scored the winning goal.
A soft free kick awarded in the visitors favour saw Rovers deal with the initial danger but as Zhirkov sent the ball across the area, Ivanovic arrived round the back to head past a helpless Robinson.
Chris Samba joined the front men for the final minutes of the game, but Chelsea were able to see the game out to claim an undeserving three points.
ROVERS: Robinson, Salgado, Samba (c), Nelsen, Givet (sub Olsson 35 mins), Jones, MB Diouf, Emerton, Pedersen, EH Diouf (sub Dunn 80 mins), Benjani (sub Roberts 46 mins).
Subs not used: Bunn (GK), Kalinic, Grella, Hoilett.
CHELSEA: Cech, Ivanovic, Cole, Essien, Drogba, Mikel, Malouda (sub Sturridge 72 mins), Zhirkov, Terry (c), Alex, Anelka (sub Ferreira 90 mins).
Subs not used: Turnbull (GK), Bosingwa, Kalou, Kakuta, McEachran.
Booked: Salgado, Nelsen (Rovers), Drogba, Ivanovic (Chelsea).