Rennes are 11th in Ligue 1 while Kiev are second behind Shakhtar Donetsk in the Ukrainian Premier League.
The Premier League clubs avoided Serie A’s second and third-placed sides Napoli, who face FC Salzburg, and Inter Milan, who play Eintracht Frankfurt.
Arsenal boss Unai Emery’s former club Sevilla face Slavia Prague and Celtic’s conquerors Valencia play FC Krasnodar.
The Gunners beat BATE Borisov 3-1 on aggregate in the last round while Chelsea eased past Malmo 5-1 over two legs.
The Blues won the competition in 2013 while Emery led Sevilla to victory in the Europa League in the subsequent three years.
Europa League last-16 draw
Eintracht Frankfurt v Inter Milan
Dinamo Zagreb v Benfica
Napoli v FC Salzburg
Valencia v FC Krasnodar
Sevilla v Slavia Prague
Zenit St Petersburg v Villarreal