An organic–inorganic photovoltaic electrode consisting of graphene nanosheets, zinc sulfide nanoparticles (ZnS) and polypyrrole nanotubes (PPy) was fabricated on indium tin oxide (ITO) glass using layer-by-layer electrophoretic deposition. The morphology and structure of the as-fabricated electrode were confirmed by X-ray diffraction, high resolution transmission electron microscopy, energy dispersive X-ray analysis, Fourier transform infrared spectroscopy and Raman spectroscopy. The photovoltaic properties of the ZnS, ZnS/PPy (ZP) and graphene/ZnS/PPy (GZP) ternary composite films modified on ITO electrodes were investigated for their solar cell performance. Both transient photocurrent and current–voltage curve measurements illustrated that the photocurrent and the power conversion efficiency of the GZP ternary composite film were significantly enhanced compared to the ZnS and ZP films. Based on these results, PPy nanotubes are an excellent sensitizer and hole acceptor, ZnS nanoparticles act as a bridge and graphene nanosheets are an excellent conductive collector and transporter, which means that, altogether, this combination of materials can significantly increase the photovoltaic efficiency.