A simple hydrothermal method of preparing highly photocatalytic graphene-ZnO-Au nanocomposites (G-ZnO-Au NCs) has been developed. Zinc acetate and graphene oxide are reduced by catechin to form graphene-zinc oxide nanospheres (G-ZnO NSs; average diameter of (45.3 ± 3.7) nm) in the presence of ethylenediamine (EDA) as a stabilizing agent and gold nanorods (Au NRs) at 300 °C for 2 h. Then Au NRs are deposited onto as-formed G-ZnO NSs to form G-ZnO-Au NCs. Upon ultraviolet light activation, G-ZnO-Au NCs (4 mg mL(-1)) in methanol generates electron-hole pairs. Methanol (hydroxyl group) assists in trapping holes, enabling photogenerated electrons to catalyze reduction of nitrobenzene (NB) to aniline with a yield of 97.8% during a reaction course of 140 min. The efficiency of G-ZnO-Au NCs is 3.5- and 4.5-fold higher than those provided by commercial TiO2 and ZnO NSs, respectively. Surface assisted laser desorption/ionization mass spectrometry has been for the first time applied to detect the intermediates (nitrosobenzene and phenylhydroxylamine) and major product (aniline) of NB through photoelectrocatalytic or photocatalytic reactions. The result reveals that the reduction of NB to aniline is through nitrosobenzene to phenylhydroxylamine in the photoelectrocatalytic reaction, while via nitrosobenzene directly in the photocatalytic reaction. G-ZnO-Au NC photocatalyst holds great potential in removal of organic pollutants like NB and in the production of aniline.