The 35-year-old played his part in a 3-0 victory over Sweden that put China on the verge of a clean sweep in the French capital, although the matches were closer than the result suggests.
Ma's sixth gold took him past divers Wu Minxia and Chen Ruolin, and gymnast Zou Kai, with the most golds of any Chinese athlete in Olympic history.
As well as his record haul of Olympic golds, Ma has also won an astonishing 14 world titles and was China's male flag-bearer at the opening ceremony.
With a wealth of options at their disposal, China controversially overlooked Ma for the singles in Paris, denying him the chance to win a third gold in a row in that event.
In his absence, Fan Zhendong won gold instead.
In the first match of the final, Ma paired up with Wang Chuqin, who had his bat accidentally broken by an overeager photographer earlier at the Games.
The Chinese duo raced into a 6-1 lead in the opening game, only for Anton Kallberg and Kristian Karlsson to fight back and take the game 11-8.
The South Paris Arena was full to capacity, and the overwhelming majority was supporting China, many of them decked out in the country's red.
They willed Ma and Wang to victory in the next game, but with little to decide between the two pairs, they went to a deciding fifth game.
Fittingly, Ma hit the winning shot with a howitzer of a forehand down the middle to put China 1-0 up in the final and on their way to another gold.
It is unclear how much longer Ma will play for.
At last year's Asian Games on home soil, having won team gold to add to his haul, he said that "this could well be my last edition of the Asian Games".
China, the unrivalled superpower of table tennis, have now won mixed doubles, women's singles, men's singles and men's team events in Paris.
In the last final, on Saturday, China play Japan for the women's team crown.
China arrived in Paris having won 32 of the 37 available golds since it became an Olympic sport in 1988.
The only other countries to have won gold are South Korea (three), and Japan and Sweden (both one).
