Primorac, like Belgian Jean-Michel Saive and Swede Jorgen Persson, has played in every Games since the sport became part of the line-up in Seoul 1988.
Yet the Croatian 43-year-old, who entered the fray in round two due to his higher ranking, was not able to claim a victory in London as Egyptian Lashin produced a superb performance to edge the decider in a seven-game thriller.
Host Nation supporters roared Great Britain's Paul Drinkhall to a shock 4-1 success against Singapore's Yang Zi.
Soon after the Brit's triumph, Saive was knocked out via a 4-1 loss against Kalinikos Kreanga.
A disappointing day for the veterans was then finished off when Persson, who finished fourth at Beijing 2008, was whitewashed by Croatia's Andrej Gacina.
Oleksandr Didukh suffered the same fate against Austria's Chen Wiexing.
I give a lot of thanks to the crowd; it was a great experienceQuadri Aruna
Daniel Zwickl produced an outstanding performance to overcome Serbia's Aleksandar Karakasevic, who sits 89 places higher in the ITTF world rankings.
Australian William Henzell upset the odds to continue his Olympic Games journey, beating Portuguese world number 39 Joao Monteiro 4-2.
Fans' favourite Quadri Aruna initially threatened another shock victory, this time versus Turkey's Bora Vang, only to falter.
Henzell said: 'I give a lot of thanks to the crowd; it was a great experience.'