Analotiy Tymoshchuk gave the hosts the lead with a long-range shot in the 54th minute but France responded in style with Lorient striker Kevin Gameiro equalising. Martin struck twice late on either side of a goal by Younes Kaboul.
Oleg Blokhin's Ukraine will play at least two matches in Donetsk next year but they will hope for an improvement between now and then after being humbled by France.
The first half was mainly forgettable although Ukraine went close to breaking the deadlock after 41 minutes when Oleg Gusev raced unmarked through the midfield but fired wide.
Ukraine went ahead when France goalkeeper Steve Mandanda could do nothing to stop Bayern Munich midfielder Tymoshchuk's thunderbolt flying into the net.
Gameiro forced a save from Andriy Pyatov soon after but France were level after 58 minutes when he seized on a deflection off a defender to smash a shot into the top corner.
Real Madrid's Benzema twice threatened Ukraine's goal but it was substitute Martin, a 76th minute substitute for Yohan Cabaye, who put France ahead in the 86th minute with a low shot into the corner.
Kaboul then outjumped his marker to head in the third goal from Martin's corner and Sochaux's Martin completed his remarkable cameo with a neat finish past Pyatov.
It was a timely win for France after they were held to a 1-1 draw with Belarus in a Euro 2012 qualifier last week.
