CuxIn1-xSe2 nanostructures have been synthesized chemically using Polyvinyl Pyrrolidone (PVP) as capping agent by varying the Cu/In composition ratio. XRD results confirm the formation of cubic CuSe2 and that of wurtzite phase of CuxIn1-xSe2 nanostructure. SEM and TEM images showed spherical shaped particle distribution of CuSe2 and hexagonal sheet/plate shaped CuxIn1-xSe2 nanostructures which are in well agreement with XRD pattern. EDAX spectra for both the structures confirm the presence of Cu, In & Se atomic(%) along with some impurity atoms. Optical band gaps calculated from Tauc plots are found to decrease from 2.5 eV to 1.4 eV from CuSe2 to In-rich CuxIn1-xSe2 samples. The conductivity of the samples shows a significant increase of current with the increase of Indium composition which are co-related with the optical band gap of the samples. A comparative analysis has also been done on Schottky and hetero structure of the CuxIn1-xSe2 samples for suitable application in photovoltaic device. The performance of CuxIn1-xSe2 nanostructures has been analyzed through photo-response studies under illumination of 546 nm monochromatic light for their fruitful application in photoconductive devices. The efficiency of devices is found to increase with % of Indium.