The invention provides a method of using 1, 1, 2, 2-polytetrafluoroethylene ethyl methyl ether as foaming agent to prepare hard polyurethane foam polyalcohol composite for the refrigerating industry, wherein the hard polyurethane foam polyalcohol composite is formed by polyether polyalcohol compound, catalysts, foam stabilizers, flame retardant and the like which have average functionality degree more than 3. Organic alkene compound (alpha-methyl styrene), N-replaced cyclohexylamine, triazine compound and the like are used as catalysts, and the composite has excellent liquidity, storage stability and demoulding performance, the foam porous structure is uniform and densely fine, and physical and mechanical performances of foam materials are excellent.