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The encounter happened just minutes after Mr Key had yet again faced questions over a dinner Justice Minister Judith Collins had with Mr Shi and a Chinese border official while in China last year.
Mr Shi and Oravida's managing director Julia Xu attended a function for about 250 dairy exporters at the Four Seasons Hotel in Beijing last night.
They declined to speak to media, saying they were there to support New Zealand dairy exports and enjoy the dinner.
However, Mr Shi lined up for a photo with Mr Key, who went to the function straight from dinner with China's President Xi Jinping.
Mr Key has met Mr Shi before - including playing a game of golf which Shi won in a fundraising auction for the National Party.
Mr Key said he had not know whether it was a National Party fundraiser at the time, or how much Mr Shi paid for the game, but Oravida's donations had been declared.
Just before the photo, Mr Key had had to defend Ms Collins to media again after further questions were raised about the dinner. He said beforehand he would be happy to meet Mr Shi, saying Oravida was a legitimate business and Mr Key had no conflict of interest.
Mr Key said that what Ms Collins had told him about the dinner was consistent with what she had said in Parliament yesterday. Asked about Ms Collins lodging a formal complaint against TVNZ for its coverage, Mr Key said he had not seen the report in question.
"In the end I leave ministers to deal with their own situations."
Mr Key has reprimanded Ms Collins for failing to advise him about the dinner earlier and not effectively managed the potential perception of a conflict of interest.
Mr Key also revealed he had spoken to New Zealand's ambassador in Beijing, Carl Worker, briefly about the dinner. Mr Worker had been invited but had not attended. Mr Key said Mr Worker was also a personal friend of Mr Shi's but had not attended because the dinner was a private dinner.
He said he did not know if Mr Worker had raised any concerns or given any advice to Ms Collins about the wisdom of the dinner or attendance of the Chinese official.
"His main point was that she's been a good minister, she did a lot of hard work up here, she's been very pro the relationship with China. But he would acknowledge he's got a personal relationship with Stone Chi."
Mr Key said with the benefit of hindsight, such matters would have been dealt with differently.
- Claire Trevett of the New Zealand Herald