Ryu Seung Min of South Korea took gold in the men's table tennis singles with a dramatic win over China's Wang Hao.
Hao was looking to complete a clean sweep of gold medals for China after victories in the women's singles and both doubles competitions.
Chinese domination of the event came to an end as third seed Ryu edged to an 11-3 9-11 11-9 11-9 11-13 11-9 victory.
Top seed Wang Liqin of China took bronze with a comfortable win over Sweden's Jan-Ove Waldner.
South Korea's Ryu repeatedly fought back in the final as Wang started each game strongly and secured victory with a huge forehand.
"Even though I won, I have to admit that Hao is a better player than I am," said Ryu.
"It's just that he was under a lot more pressure than I was."
Coming into Athens, China had won 13 of the 16 golds since the sport was added to the Olympic
program in 1988.
Zhang Yining added women's singles gold on Sunday, after she and Wang Nan won the women's doubles, and Chen Qi and Ma Lin took the men's doubles.
"We won all the (four) golds in 1996, we won all the (four) golds in 2000 and we won three golds here so we are still the strongest and most invincible team," said Hao.
Liqin recovered from his surprise semi-final defeat to see off 38-year-old Waldner 10-12 11-3 11-8 11-7 11-9.
The defeat ends the Olympic career of 1992 champion Waldner, but he will play on next year.
"It would have been fun to have won the bronze but life goes on," said Waldner. "I'm going to rest for a while then start training again in September.
"I will compete at next year's world championships but I'm not going to take part in the 2008 Olympics."
The International Table Tennis Federation (ITTF) wants to drop the doubles competition from the Olympic schedule.
ITTF president Adham Sharara has put forward a proposal to the International Olympic Committee to replace the pairs with a team event.
Sharara also responded to claims China's dominance was unhealthy for the future of the sport.
"Things are only going to change when other countries do as much preparation, training and infrastructure works a the Chinese do," said Sharara.