The invention provides a production method of a polyurethane composite for shoe materials. The production method generally includes the steps: (1) hydrolyzing ethyltrichlorosilane prior to reacting with potassium hydroxide serving as a catalyst to obtain POSS (polysilsesquioxane); (2) subjecting the POSS, propylene oxide, dipropylene glycol, dibromo butyl diol and carbon dioxide to reaction through a DMC catalyst so as to obtain PPC (polypropylene carbonate); (3) uniformly mixing the PPC, a surfactant, a catalyst, an opening agent, a chain extender and a forming agent to prepare a mixture; (4) mixing isocyanate with the mixture prior to casting, demoulding and curing so as to obtain the polyurethane composite for the shoe materials. The polyurethane composite prepared through the method has good flame retardancy and heat resistance.