Arsenal took an early lead but a red card for Sokratis Papastathopoulos changed the game as the Gunners slumped to a 3-1 defeat at Rennes.
In all, it was a night of tightly-contested Europa League last 16 first leg ties on Thursday.
Villarreal and Dinamo Zagreb also won and the other two early games, Sevilla versus Slavia Prague and Eintracht Frankfurt versus Inter Milan, ended all square.
Arsenal had never lost to French opposition away from home in 12 previous European games and they took an early lead.
What looked like a cross from Alex Iwobi evaded everyone and sneaked in at the far post early on.
Playing in their change turquoise-green shirts, the English side looked to be in control.
However, the match changed completely four minutes before half-time when Papastathopoulos was sent off for a second bookable offence.
Rennes equalised from the resulting free-kick when Benjamin Bourigeaud rifled home at the second attempt and they came out for the second half looking far more positive than the London side.
The French side went ahead 20 minutes into the second half when Mehdi Zeffane’s shot looped off defender Nacho Monreal into the net.
Ismaila Sarr made it 3-1 two minutes from time when he powered home a header from a lovely curling left-wing cross.
Callum Hudson-Odoi scored his third Europa League goal of the season as Chelsea beat Dynamo Kiev in their last-16 first-leg match to move closer to the quarter-finals.
The lively Pedro opened the scoring from close range as he ran on to Olivier Giroud’s backheel, BBC reports.
Willian struck the second goal Chelsea’s dominance deserved as he curled home from 25 yards.
Teenager Hudson-Odoi added a late third to put Chelsea in control of the tie.
Dynamo Kiev – who have never won in their 15 visits to England – did not manage a shot on target.
The second leg is at Kiev’s Olympic Stadium next Thursday at 17:55 GMT.
The Blues, who won the Europa League in 2013, may need to win the tournament to qualify for next season’s Champions League as they are sixth in the Premier League.
Maurizio Sarri made six changes but still named a relatively strong team, with Eden Hazard, N’Golo Kante and Gonzalo Higuain on the bench in case of emergency.
Pedro scored the opener when he moved in from the left and played a one-two with Giroud before placing the ball through the legs of goalkeeper Boyko.
He then missed a glorious chance to double the lead as he fired straight at the keeper from six yards from Davide Zappacosta’s cross.
Ross Barkley had a shot stopped by the goalkeeper’s legs, before Pedro had a volley and 18-yard effort saved.
After the break, the ex-Barcelona winger again tested Boyko as he cut in from the right but his low effort was stopped.
It looked at that stage like Chelsea might be going to Ukraine with only a one-goal lead, but then Willian stepped up with a free-kick which left Boyko rooted to the spot.
Hudson-Odoi scored after a pass from fellow substitute Ruben Loftus-Cheek late on to put Chelsea on the brink of the last eight.
Kepa Arrizabalaga, who kept his place in goal, was not needed to make a save, although he flapped at a cross late on.
