The Blues were part of the first tie drawn out on Friday lunchtime, and will have to travel to Ukraine in the second leg – a 3,000-mile round trip.
The Gunners meanwhile will face Ligue 1 club Rennes, who beat Real Betis in the round of 32.
EUROPA LEAGUE LAST 16 DRAW
Chelsea v Dynamo Kiev
Eintracht Frankfurt v Inter Milan
Dinamo Zagreb v Benfica
Napoli v Red Bull Salzburg
Valencia v Krasnodar
Sevilla v Slavia Prague
Arsenal v Rennes
Zenit v Villarreal
First leg ties take place on March 7, second leg games on March 14.
DYNAMO KIEV FACTS
Stadium: NSK Olimpisky, with a capacity of 70,050
Best player: Ukraine international winger Viktor Tsyhankov, 21
Manager: Aleksandr Khatskevich
How they got here: Eliminated in Champions League qualifying by Ajax, they came through a Europa League group containing Rennes, Jabonlec and Astana, before beating Olympiakos in the round of 32.
Stadium: Roazhon Park, with a capacity of 29,778
Best player: Senegal international winger Ismaila Sarr, 20
Manager: Julien Stephan
How they got here: Entered into the Europa League group stage, they finished second in Group K behind Dynamo Kiev. Won an exciting round of 32 tie with Real Betis – 3-3 in the first leg, before winning 3-1 in Spain.
The Gunners were drawn out first and were initially set to play the first leg of the tie at the Emirates Stadium, however the club said they have agreed with Rennes to flip the tie, with the opening fixture to be played in France.
The first leg will take place on Thursday, March 7, with kick-off at 5.55pm UK time at Roazhon Park, where England played Wales in Euro 2016.
Arsenal host the return leg at the Emirates on Thursday, March 14, with kick-off at 8pm in north London.
Chelsea came through their round of 32 tie against Malmo with relative ease, winning 5-1 on aggregate, while Arsenal had to come from behind against BATE Borisov – they lost 1-0 in Ukraine, but won the second leg 3-0 in north London.