CuS decorated TiO₂ nanofibers were successfully prepared by the combination of electrospinning and hydrothermal processes. The TiO₂ nanofibers were prepared via heat treatment of polyvinylpyrrolidone (PVP)/tetrabutyl titanate (Ti(OBu)₄) composite nanofibers which were prepared through sol–gel processing. SEM (scanning electron microscopy) and TEM (transmission electron microscopy) images reveal that the diameters of TiO₂ nanofibers are <100 nm and that island-like CuS particles attached to the TiO₂ nanofibers form the heterostructure. The heterogeneous catalytic properties of the as-prepared samples were evaluated via methyl blue dye decomposition and the samples showed enhanced photocatalytic activity for the degradation of a simulation of pollutants.