Polyurethane acrylate (PUA) and o-cresol formaldehyde epoxy resin (o-CFER) is synthesized. The PUA/o-CFER glass fiber-reinforced composites cured by free radical/cationic ring-opening reaction are modified by the reducing graphene oxide (r-GO). Effect of r-GO on the thermal and mechanical properties of PUA/o-CFER glass fiber-reinforced composites are characterized by FTIR, DMA and TGA. The result of FTIR shows that the system has cured completely. DMA analysis indicates that this system has better compatibility, and the glass transition temperature (T (g)) decreases with increasing r-GO content. TGA analysis shows that the initial thermal degradation temperature (T (id)) and activation energy (E (a)) enhance 13.1 A degrees C and 3.12 kJ/mol, respectively. The tensile and impact strength of glass fiber-reinforced composites are approximately 50 and 60 % higher than those without r-GO. It is shown that the r-GO can enhance the mechanical properties and thermal stability of composites.