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Blackburn dumped Chelsea out of the Carling Cup in a penalty shoot-out to set up a semi-final with Aston Villa.
Nikola Kalinic put Rovers ahead from six yards before a header from substitute Didier Drogba and Salomon Kalou's finish sent Chelsea in front.
Hilario failed to deal with a deflected Brett Emerton cross and Benni McCarthy scored a penalty, but Paulo Ferreira levelled at 3-3 deep into extra-time.
Gael Kakuta missed the crucial spot kick as Rovers won the shoot-out 4-3.
The 18-year-old Kakuta, who Chelsea controversially signed from Lens, struck the ball straight at Paul Robinson, who had earlier sensationally tipped Michael Ballack's spot kick on to the post.
Premier League leaders Chelsea went into the tie unbeaten in nine games while Carlo Ancelotti's team had not conceded in their previous four matches.
But the Italian will not be winning the Carling Cup in his first season in English football after his team produced a largely below-par performance at Ewood Park.
After a disjointed first-half, the Londoners did improve, scoring twice in four minutes to take a 2-1 lead.
Ancelotti had made a bold triple substitution at half-time but when Kalou limped off midway through the second half, Chelsea were reduced to 10 men.
By that stage Rovers had levelled and went on to capitalise on their numerical advantage when McCarthy struck, but Chelsea's refusal to throw in the towel ensured the tie went the full distance.
The victory was sweet revenge for Blackburn, who lost 5-0 at Stamford Bridge in the Premier League, and a real tonic for manager Sam Allardyce as he recovers from heart surgery.
There was certainly much to admire in an old-fashioned cup tie that started at a fast and frenetic piece, with both teams showing a willingness to attack from the opening whistle.
The lively Kalinic shot wide under pressure from Ferreira shortly before his ninth-minute opener.
It was a well-constructed goal that saw Morten Gamst Pedersen play in Pascal Chimbonda, who in turn drilled the ball low across the face of goal for Kalinic to slot home.
If it was a simple finish in the end by the Croatia international, he did well to get in front of Zhirkov.
Chelsea had been unusually wasteful in possession and struggled to create clear-cut openings. Even so, Kalou, Jon Obi Mikel, Joe Cole, Ballack and Zhirkov all either forced regulation saves from Robinson or missed the target before the break.
Kalou's miss was the most glaring, heading wide from six yards at the far post after an inviting cross from Juliano Belletti.
Ancelotti's thoughts on Chelsea's first-half performance were reflected in his decision to introduce Jeffrey Bruma, Kakuta and Drogba.
Ivory Coast international Drogba had been spotted with a hot-water bottle as he watched from the dugout during the opening half but it did not take him long to get warmed-up.
On the pitch for just three minutes, Drogba climbed above Ryan Nelsen to head home Malouda's cross.
And after 52 minutes Chelsea took the lead when Zhirkov collected a loose ball and released Kalou, who closed in on goal with his first two touches before slotting the ball beyond Robinson.
There was a lengthy interruption following a nasty collision between Kakuta and Steven N'Zonzi but it did not holt Chelsea's momentum and Kalou should have added a third with a free header.
Rovers levelled when Kalinic attempted to head Emerton's deflected cross at the near post. It was difficult to conclude whether the Croatian actually touched the ball but either way it eluded Hilario.
Chelsea were reduced to 10 men when Kalou limped off and their dominance of the game was considerably reduced.
Rovers thought they had snatched a dramatic victory in injury-time but McCarthy's effort was ruled out for offside.
Kalinic then forced a good save from Hilario but Chelsea survived to take the match into extra-time.
Rovers pressure eventually told when the home team regained the lead from the penalty spot early in extra-time.
Zhirkov, who had a very mixed evening, clearly fouled substitute David Hoilett and McCarthy sent Hilario the wrong way from the penalty spot.
Ferreira equalised with just about the last action of extra time with a neat finish from a tight angle after Robinson had flapped at a cross.
But Rovers held their nerve in the penalty shoot-out to seal a place in the last four.
Source: bbc
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