Nano graphene oxide (NGO) was produced by further refluxing graphene oxide (GO) sheets in HNO3, and carboxylic acid functionalized graphene oxide (GO–COOH) was obtained by a simple etherification reaction between GO and chloroacetic acid. The GO, GO–COOH and NGO sheets are combined with TiO2 nanorods by a two-phase assembling method, and confirmed by transmission electronic microscopy. The GO–TiO2, GO–COOH–TiO2 and NGO–TiO2 composites are used in a comparative study of photocatalytic H2 generation activity under UV light irradiation. The H2 generation rate of TiO2 nanorods was slightly increased from 15 to 30 mL h−1 g−1 by replacing oleic acid ligands with hydrophilic dopamine, and significantly increased to 105 mL h−1 g−1 after combining with GO sheets. The further comparative study shows that GO–COOH–TiO2 composite has higher H2 generation rate of 180 mL h−1 g−1 than that of GO–TiO2 and NGO–TiO2 composites.