Lee Bo went missing Wednesday night and is the fifth employee of Hong Kong-based publisher Mighty Current to disappear.
The incident adds to growing unease that freedoms in the semi-autonomous Chinese city are being eroded, with fears the five men may have been detained by Chinese authorities.
"He said he wouldn't be back so soon and he was assisting in an investigation," Lee's wife Sophie Choi told Hong Kong's Cable Television, describing a call she had with Lee the night he failed to return home.
"I asked him if it was related to the case before. He said 'yes', regarding that case where a few others had gone missing," Choi said.
Police said in a statement they were investigating the disappearance of Lee and three of the other missing men.
It made no comment on the fifth man.
Deputy leader Carrie Lam tried to reassure the public.
"The Hong Kong government cares about its people's wellbeing... Police are working on this case," she told reporters.
Choi previously told AFP she started looking for Lee on Wednesday night after he failed to return home for dinner and she reported him missing to police on Friday.
Another source told AFP that Lee, 65, was last seen in Hong Kong on Wednesday at the publisher's warehouse, which he is in charge of.
Hong Kong was handed back to China by Britain in 1997 and enjoys liberties not seen on the mainland, but there are fears these are under threat.
The publishing company's general manager Lui Bo, an employee Cheung Jiping and bookstore manager Lam Wing-kei are also apparently missing after disappearing in southern China in October.
Hong Kong police are investigating the disappearance of Lui, Cheung, Lam and Lee -- they gave no information on Gui.
Sweden's embassies in Bangkok and Beijing are reportedly investigating Gui's disappearance.
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