Roman Zozulya's second-half strike put Ukraine firmly in control of their World Cup qualification hopes as they went on to beat France 2-0 in their first leg play-off tie on Friday.
Zozulya struck in the 61st minute before Andriy Yarmolenko's penalty left the 1998 World Cup winners and 2006 finalists firmly on the back foot ahead of the second leg in France next Tuesday.
France defender Laurent Koscielny had a second half to forget as he not only conceded the 83rd-minute penalty but was shown a red card in stoppage time, with Ukraine defender Olexander Kucher following soon after for his second bookable offence.
In a team dripping with talent, France were expected to bring to an end Ukraine's seven-game run of successive clean sheets while moving one step closer to next year's World Cup finals in Brazil.
However, it was Ukraine who claimed the advantage in Kiev leaving Didier Deschamps' men with little time to regroup ahead of the rematch.
Arsenal striker Olivier Giroud had tested Ukraine goalkeeper Andrei Pyatov with a header, only for the stopper to make a comfortable save, before Paul Pogba saw his 30-yard effort blocked by Artem Fedetskiy.
Other than that, chances were few and far between in the first half until Yevhen Konoplyanka forced a block from Eric Abidal in the 39th minute, with Patrice Evra clearing Ruslan Rotan's subsequent corner.
After the break, Franck Ribery saw his corner chance caught by Pyatov before he drilled a free-kick into the Ukraine wall from 25 yards out soon after.
At the other end, defender Fedetskiy fired a long range effort of his own over the bar before France keeper Hugo Lloris caught Yevhen Konoplyanka's 56th-minute effort.
Ukraine midfielder Edmar then served up the pass that would set up Zozulya for the only goal of the match.
The Brazilian-born Ukrainian set up Zozulya from the centre of the area, allowing the Dnipro Dnipropetrovsk striker to slot the ball past Lloris from 12 yards.
Zozulya had another chance denied two minutes later after an Abidal block as Ukraine looked to claim momentum.
Ribery remained a pest at the set piece, although Yevhen Khacheridi was able to clear his corner before Samir Nasri saw his 20-yard effort saved by Pyatov.
Ribery tried his luck from similar distance but he too was denied by Pyatov, before Koscielny put his header wide from another corner from the Bayern Munich midfielder in the 80th minute.
Things then went from bad to worse for Arsenal defender Koscielny when he conceded a penalty for a foul on Zozulya, with Yarmolenko stepping up to blast the ball past Lloris and claim a two-goal advantage.
The game was shortly over for the France defender when he was shown a red card in the 90th minute for needlessly hitting out at Kucher.
Kucher was sent off himself in the fifth minute of stoppage time for his second yellow card offence for a challenge on Ribery.
Greece 3-1 Romania
Kostas Mitroglou narrowly missed a hat-trick as Greece beat Romania 3-1 in the first leg of a World Cup qualifying playoff tie at the Georgios Karaiskakis stadium in Athens on Friday.
The Olympiakos Piraeus striker volleyed Greece in front after 14 minutes but the visitors hit back four minutes later via Bogdan Stancu's header from a clever Gabriel Torje free-kick.
The Greeks retook the lead immediately with a Dimitris Salpingidis close-range finish, while Mitroglou added a third in the 66th to increase the advantage. Romania's Costin Lazar was then sent off in stoppage time.
Fernando Santos' team were well worth the victory that gave them every chance of securing a place in Brazil next year after the return leg against Victor Piturca's Romania in Bucharest next Tuesday.
Iceland 0-0 Croatia
Ten-man Iceland hung on for a heroic 0-0 draw in the first leg of their playoff with Croatia on Friday to keep alive their dream of reaching the World Cup finals for the first time.
Croatia had the upper hand in the opening 20 minutes but the home team dealt with the pressure comfortably before establishing their own more direct passing game as the half went on.
Iceland were then hit by a double blow when forward Kolbeinn Sigthorsson went off injured just before halftime and Olafur Skulason received a straight red card five minutes into the second period.
Skulason was dismissed for tangling with Ivan Perisic when the Croatian was through on goal.
The sides meet again in the return leg in Zagreb on Tuesday.