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The pair, aged 56 and 28, were rescued by emergency services from Queen's Dock on the River Mersey in the Port of Liverpool at 4.30pm yesterday (25th February).
The two men were taken to hospital but the older man died last night, Merseyside Police said.
His family is being informed and a post-mortem examination will be carried out.
The 28-year-old remains in hospital in a stable condition.
Last night a police cordon was in place around the scene as officers carried out investigations, and the man's death is being treated as unexplained.
The Merseyside force is appealing for witnesses on 101.