•A new multi-component photocatalyst with hierarchical nanostructures is developed.•Graphene, TiO2 nanowires and Pd nanoparticles are integrated.•Enhanced light harvesting efficiency in the visible-light region was witnessed.•Kinetics of the photocatalytic reduction of 4-nitrophenol were studied.•Photosynergistic roles are identified. In this work, a new hybrid nanocatalyst, namely titanium dioxide (TiO2) composite nanowires, encapsulated with graphene (G) and palladium nanoparticles (Pd NPs) (designated as G-Pd@TiO2-CNWs), was prepared. In preparing the nanowires, a combination of electrospinning and hydrothermal approaches was employed. The visible-light-driven photocatalytic performance of G-Pd@TiO2-CNWs was investigated using the reduction of 4-nitrophenol (4-NP) as a model reaction. The results showed that G-Pd@TiO2-CNWs converted nearly 100% of 4-NP under visible light irradiation. The reaction kinetics of the photocatalytic reduction of 4-NP was studied by UV–vis spectrophotometry and the apparent rate constant was determined and compared with those for other supported TiO2 catalysts. Furthermore, the spent G-Pd@TiO2-CNWs could be recovered by simple centrifugation and reused. The work is expected to shed new light on the development of G-incorporated hybrid nanostructures for harvesting light energy and on the development of new photocatalysts for the removal of environmental pollutants.