The Serb staved off two set points in the opening stanza then stepped up a gear and never looked back.
The 22-year-old Frenchman, playing in just his second ATP Tour main draw event, saved two match points at 5-2 down in the second set but could not stave off defeat for long and Djokovic closed out the victory in just over 90 minutes.
The 2009 Paris champion next faces either American 13th seed John Isner or Polish qualifier Michal Przysiezny in the round of 16.
Britain's Andy Murray, third in the ATP Race to London, has withdrawn because he is still recovering from back surgery, meaning the ninth-ranked player will qualify for the O2 event.
Swiss Roger Federer, who is seventh in the Race, will qualify if he wins his first match at Bercy after a bye into the second round.
Paris Masters results
2-Novak Djokovic (Serbia) beat Pierre-Hugues Herbert (France) 7-6(3) 6-3
Kei Nishikori (Japan) beat 8-Jo-Wilfried Tsonga (France) 1-6 7-6(4) 7-6(7)
14-Jerzy Janowicz (Poland) beat Santiago Giraldo (Colombia) 7-6(3) 6-3
9-Richard Gasquet (France) beat Fernando Verdasco (Spain) 7-5 6-7(6) 6-3
Kevin Anderson (South Africa) beat Mikhail Youzhny (Russia) 4-6 7-6(0) 2-1 (Youzhny retired)
Marcel Granollers (Spain) beat Dmitry Tursunov (Russia) 6-4 6-4
Ivan Dodig (Croatia) beat Edouard Roger-Vasselin (France) 7-6(6) 6-4
Pablo Andujar (Spain) beat Vasek Pospisil (Canada) 6-4 2-6 6-4
Nicolas Mahut (France) beat Alexandr Dolgopolov (Ukraine) 7-6(6) 6-1
Grigor Dimitrov (Bulgaria) beat Michael Llodra (France) 6-7(5) 6-3 6-3
Michal Przysiezny (Poland) beat Jarkko Nieminen (Finland) 6-3 7-6(6)