Chelsea, whose defeat was compounded by the loss of goalkeeper Petr Cech with a calf injury in the second half, were a goal down inside three minutes when striker Diego Milito put Inter ahead. Salomon Kalou equalised in the 51st minute but Mourinho's men restored their advantage four minutes later when Esteban Cambiasso drilled in the winner.
Kalou's goal may yet prove to be the pivotal moment of the tie when the two teams meet again in the return leg at Stamford Bridge next month.
A match that had been built-up as a contest between the two coaches – Blues manager Carlo Ancelotti was returning to his former home – was sparked into life inside three minutes. Thiago Motta's through ball found Milito inside the Chelsea area and when captain John Terry half-heartedly attempted to block Milito's progress, the Inter striker slammed the ball beyond Cech at the near post. Mourinho greeted the goal with an approving nod from his seat in the Inter dugout.
Chelsea won a free-kick some 35 yards out when Dejan Stankovic fouled Michael Ballack in the 15th minute and they were unlucky not to equalise. Didier Drogba's fierce attempt on goal cannoned back off the crossbar with Julio Cesar well beaten. In the 22nd minute goalscorer Milito was booked for diving after going down from an imaginary challenge by Ricardo Carvalho and Kalou followed him after a foul on Wesley Sneijder.
Apart from Milito's goal, Chelsea had looked untroubled in defence and had dominated possession. John Obi Mikel sent a rising drive into the arms of Cesar in the 29th minute as Chelsea continued to press for a leveller.
But Inter spurned a gilt-edged chance to increase the lead in the 34th minute when Sneijder's cross found Samuel Eto'o unmarked on the edge of the six-yard box. But instead of planting the ball past Cech, Eto'o missed his kick.
Chelsea should have been awarded a penalty seconds before the interval when Kalou went down under a challenge from Walter Samuel. But their claims were denied by referee Manuel Gonzalez. But in the 51st minute Chelsea were level through Kalou. Branislav Ivanovic created the opportunity when he ran unchallenged to the edge of the Inter area. The Chelsea right-back looked to have over-run the ball but managed to turn it into the path of Kalou, who curled it in from the edge of the box. Kalou and the rest of the Chelsea squad then ran to the dugout in a clear show of support for Ancelotti.
It took Inter just four minutes to re-establish their lead. Ivanovic blocked Cambiasso's first attempt but there was little anyone could do about the follow-up shot which flashed into the bottom corner beyond Cech from 18 yards.It got worse for Chelsea on the hour when goalkeeper Cech had to be stretchered off after rolling the ball out. There was nobody around the Czech Republic international when the incident occurred and Chelsea later confirmed Cech had suffered a calf injury, which will be monitored over the coming days, and he was replaced by Hilario.
Chelsea should have levelled in the 64th minute when Frank Lampard collected a cross from Anelka but saw his eight-yard shot saved by Cesar. Mikel summed up a night of frustration for the Blues when he sent a 20-yard shot into the stands in the 88th minute
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