City striker Edin Dzeko had admitted ex-Chelsea forward Shevchenko has always been his idol in the build-up to the game. And while the Bosnian had another quiet match, Sheva showed how it should be done with a well-taken opener and a classy all-round display.
Oleh Gusev added a second late on to give City a real mountain to climb in the return leg next Thursday. And their night was summed up by another childish display from bad-boy Italian Mario Balotelli, who clearly did not fancy the cold in the Ukraine.
City could have taken an early lead from Aleksandar Kolarov's corner but Balotelli volleyed over.
Minutes later, a clever ball by David Silva looked to have put Micah Richards clear but he was just beaten to it by Kiev keeper Alexandr Shovkovskiy.
Kolarov then found himself with a free-kick 25 yards out but his effort was straight at the home keeper.
The full-back was really in the thick of it and had another chance with a left-footed volley, which was again too close to the keeper.
Kiev put eight past Besiktas over two legs but did not fashion a single chance in the opening quarter of this.
But, when they finally dId, they took the lead as Andriy Yarmolenko held off Silva and put over a dangerous cross.
Nobody tracked Shevchenko and he got his toe in ahead of City stopper Joe Hart to score a real poacher's goal.
It was a 67th strike in European competition for Sheva, 34, who struggled so badly during his time in England with Chelsea.
He could have added to that tally just before the break but his half-volley from 18 yards whistled just over.
Kiev, who have not lost in six home European ties, then finished the opening half strongly as Gusev and Artem Milevsky both had shots which were narrowly off target.
City had been disappointing for the first 45 minutes and boss Roberto Mancini clearly thought so too as he was going mad in the dugout.
Balotelli had been as frustrating as ever and seemed reluctant to come out for the second half.
But Mancini ordered him to continue - and the ex-Inter Milan striker promptly got himself booked for a wild challenge on Ayila Yussuf.
It was no surprise then that he was hauled off on 57 minutes, to be replaced by skipper Carlos Tevez.
City seemed to have bucked their ideas up with yet another Kolarov shot being deflected over.
Then some good work by Gareth Barry on the edge of the box saw him create a chance for Yaya Toure - but his low shot was pushed round the post by Shovkovskiy.
And the visitors were left kicking themselves when Kiev doubled their lead as a cross from the right was flicked on by Milevsky.
Richards reacted too slowly and Gusev took a touch on his chest before blasting a volley past Hart.
Yussuf could have effectively ended the tie right at the death with City at full stretch but Hart made what could yet be a crucial save.
DREAM TEAM
STAR MAN - ANDRIY SHEVCHENKO (Kiev)
MAN CITY: Hart 7, Richards 5, Kompany 6, Lescott 6, Zabaleta 5, Y Toure 6, Barry 6, Kolarov 5, Dzeko, Balotelli 5, Silva 6. Subs: Tevez (Balotelli 57) 6, Wright-Phillips (Kolarov 82) 5. Subs not used: Taylor, Boateng, Boyata, Vieira, De Jong. Booked: Balotelli, Tevez.