Nanostructured conducting polymeric materials are beneficial for electron conduction and mass transport, showing high photocatalytic performance under visible light. Herein, we report a colloidal synthesis of copper and copper oxides (Cu2O) modified polypyrrole nanofibers (PPy) heterostructures, which demonstrates significantly high photocatalytic H-2 generation under visible light. The presence of Cu nanoparticles (NPs) of 50 nm and cubic shaped Cu2O nanoparticles of size 200 nm endows the heterostructures with a large specific surface area as well as good dispersion of nanoparticles on PPy nanofibers allows the migration of electron during catalysis. Cu2O/PPy exhibits excellent H-2 production (67 mmol h(-1)) which is 12 times higher than pure PPy (5.7 mmol h(-1)). The high catalytic activity of Cu2O/PPy heterostructure provides a fervent alternative to noble metal-based catalysts for the hydrogen generation and water splitting. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.