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TiO 2 nanorods decorated with CdS and Ag0 were prepared and anchored on to a fluorine doped tin oxide (FTO) electrode in order to investigate the photoelectrochemical (PEC) oxidation of nitrobenzene (NB) coupled with simultaneous reduction of water to produce molecular hydrogen (H 2). The modified TiO 2 nanorods (TiO 2 -NRs) prepared for 4 h have regular nanoroads with high superficial area and Ag nanoparticles loaded on the surface of nanoroads covered with CdS film uniformly. The nano-composite TiO 2 -NRs with photochemically active up to 700 nm with coupled photoconversion efficiencies for NB degradation and H 2 production as high as 4.4%. The surface plasmon resonance (SPR) effect of Ag not only excited the photo-generated electron of Ag nanoparticles, but also promoted the electron transfer from CdS to TiO 2 -NRs. NB as a role of electron donor, reacts with hole to improve the efficiency of H 2 production. The heterostructure electrode for solar energy conversion had an important significance for solving environmental pollution and energy crisis. Image 1 • TiO 2 nanorods decorated with CdS and Ag0 were prepared and anchored on to a FTO electrode. • Simultaneous oxidation of nitrobenzene coupled with reduction of water to produced H 2. • Ag particles loaded on the surface of TiO 2 nanoroads covered with CdS film uniformly. • Photoconversion efficiencies for nitrobenzene degradation and H 2 production as high as 4.4%. • The heterostructure of CdS/Ag/TiO 2 -NRs electrode has solar energy conversion in PEC system. [ABSTRACT FROM AUTHOR]