The Grade I listed property opened in 1911 as the headquarters of the Royal Liver Assurance Group.
Owner Royal London Group, who acquired the building in its centenary year as part of a takeover, has instructed CBRE to sell the landmark site.
CBRE said it expected the sale of the "iconic symbol of Liverpool" to attract strong interest from investors.
The building is home to the two fabled metal Liver Birds, which watch over the city and the sea at Liverpool's Pier Head.
Along with the Cunard and Port of Liverpool building, the Royal Liver building forms part of Liverpool's Three Graces.
The news follows last month's announcement that Liverpool's Grade II listed Municipal Buildings will be sold off as part of Â£90m of savings by the city council over the next three years.
Liverpool's Royal Liver building has been put up for sale for the first time in its history.