The 55-year-old was previously assistant manager at Hibernian and Inverness Caledonian Thistle and moves from St Mirren, where he was No 2 to Oran Kearney.
Rice was a player with Hibernian, Nottingham Forest, Falkirk and Dunfermline Athletic before moving into coaching with Morton in 2000.
He takes over with Hamilton sitting 10th in the Ladbrokes Premiership, one point ahead of a Dundee side who they welcome to the Hope CBD Stadium on Saturday.