He died in Prince of Wales Hospital at 8.32pm, with his family keeping him company.
The actor stopped working after he was diagnosed with cancer late last year.
Liu starred in more than 90 television drama and 70 movies in his four-decade acting career.
He won the Best Supporting Actor award twice at the Hong Kong Film Awards for Cageman (1992) and The Beast Stalker (2008).
Liu is survived by his wife, TVB leading actress Barbara Chan Man-yee.
The couple had three sons. The youngest one died at the age of five in 2006 after a three-year battle with leukaemia. The other two sons are aged 22 and 26.
His death came less than a month after veteran actor Ng Man-tat died at 70 of liver cancer.
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