The invention provides a recovery method of materials containing copper, indium, gallium and selenium. The method comprises the following steps: the materials containing copper, indium, gallium and selenium are reacted with a reducing agent to obtain gas-state selenium-contained compounds; and meanwhile, indium and gallium co-melts are obtained at a reaction temperature. The method uses the reducing agent for reducing copper, indium, gallium and selenium in the materials containing copper, indium, gallium and selenium in a simple mixing state; simple selenium is reacted with the reducing agentto generate gas-state substances for separation out; indium and gallium with lower melting points are separated from copper in a form of co-melts to obtain gas-state selenium-contained compounds andindium and gallium co-melts with relatively simple components; selenium can be recovered from smoke through subsequent treatment; indium and gallium are separated and recovered from the co-melts; andthe problems of more complex chemical components in whole recovery system and longer separation and recovery procedures in the prior art are solved.