Polymer–graphene composites have attracted significant attention; however, their formation mechanisms are a focus of debate. This work tries to clarify how grafting occurs on graphene by electron spin resonance techniques. As a result, two pathways are found. One passes through the radicals formed by cleaving C-O bonds on graphene are transferred to monomers, then grafting and polymerization proceed. Another mechanism passes through the oxy-radicals, which react with monomers in solution and finally react with carbon radicals on graphene. Based on the mechanism, various types of polymer–graphene composites are prepared, and applied to electrical conductive sheets, basic catalysts, and acidic catalysts.