In this work, pure and copper mixed oxide PAni nanofiber thin films are successfully synthesized on silicon substrates by hydrothermal method and spin coating technique at room temperature with thickness of about 325 nm. The structural, surface morphological, optical and photoconductivity properties have been investigated. The XRD results showed that PAni films have crystalline nature, CuO and PAni/CuO nanostructure composites are monoclinic polycrystalline structure. The FESEM images of PAni clearly indicate that it has nanofiber-like structure, whereas the CuO film has spongelike shape. The surface morphology analysis of PAni/CuO composite shows that nanofiber caped with inorganic material which is CuO is a core-shell structure. Optical characterization shows that the direct electronic transition is allowed in the energy gap. The values of energy gap for PAni nanofibers and CuO are 3.98 eV and 5.29 eV respectively. The spectral response of PAni nanofibers, CuO and PAni/CuO composite was studied. The values of responsivity and quantum efficiency of PAni/CuO composite are larger than those for pure PAni nanofibers. One can conclude that with mixing, the sensitivity is higher than that without mixing and is found to be 220 %. PAni/CuO composite exhibits fast rise time of 0.32 s with full time of 0.41 s, while slow rise time of 0.67 s and 0.38 s was respectively observed for PAni nanofibers and CuO with full time of 3.32 s and 1.19 s.