China's Zhang Jike eyes the ball during men's singles third round at the World Table Tennis Championships in Dusseldorf, Germany, June 2, 2017. [Photo/VCG]

Zhang, who won the championship in 2013 and 2011, was apparently not in form, making too many errors and losing to South Korea's Lee Sangsu 4-1 (9-11, 6-11, 13-11, 6-11, 10-12).

It was his earliest exit since making his singles debut at the World Championships. He was stopped at the semifinals in Suzhou, China, two years ago.

The 29-year-old Zhang, who won the gold medal in the 2012 London Olympics and silver in Rio, had a chance in the fifth game, fighting back from 3-6 down to pull ahead 10-7. But Lee, who looked steady and confident, managed to level the score at 10-10 and went on the seal his first win in their fourth meeting with Zhang.

"If I had won the last game, I might have a chance," said a disappointed Zhang.

The other four Chinese players went through to the last 16.

Defending champion Ma Long, who defeated Zhang in the Rio Olympics final, met little trouble in beating Romania's Ovidiu Ionescu 4-1.

World No 2 Fan Zhendong breezed past Russia's Alexander Shibaev 4-1 and world No 3 Xu Xin removed the last man standing from outside of Europe and Asia, defeating Hugo Calderano of Brazil 4-1.

Lin Gaoyuan, the lowliest-ranked among the five Chinese men, edged India's Sharath Kamal Achanta 4-2.

German star Timo Boll beat Jang Woojin of South Korea 4-1 while local hero Dimitrij Ovtcharov struggled into last 16 with a hard-fought 4-3 victory over Romania's Hunor Szocs.

The Chinese women proved that nobody but themselves can beat them. With all the five players reaching the quarterfinals, two of the matches became all-Chinese affairs.

World No 3 Zhu Yuling beat fifth seed Chen Meng 4-2 and second seed Liu Shiwen defeated qualifier Mu Zi 4-1.

In the other two matches, world No 1 and defending champion Ding Ning routed Japan's sixth-ranked Ishikawa Kasumi while 17-year-old Miu Hirano trounced world No 4 Feng Tianwei of Singapore.

Ding will meet Hirano while Zhu take on Liu in the semifinals.

Hirano became Japan's first singles medal winner in 48 years after moving into the semifinals and securing a bronze medal.

The last time Japan won a singles medal was back in 1969 when Toshiko Kowada won gold in Munich, Germany.

"I am so happy to win," the Asian champion said. "I did not know that it has been so long that Japan has won a medal, I am a bit surprised. I am happy to have this record, and that this will be in the history books."

Hirano defeated three Chinese players, including world No 1 Ding, en route to the Asian championship in April.