Fabrication of economically viable photocathode for hydrogen energy production through solar water splitting is a major research among the scientific community for a decade. P-type compound Cu2ZnSnS4 (CZTS) is very interesting material due to its absorption property, earth-abundant constituents and environmental friendliness that serves as a suitable candidate to act as a photocathode. In the present work, Cu2ZnSnS4 (CZTS) nanoparticles are synthesized by simple one-step chemical method and annealed at 350 °C for three different times (60 minutes, 90 minutes and 120 minutes). The effect of annealing time on the structural, optical and photoelectrochemical properties are investigated. XRD pattern indicates the formation of tetragonal crystal structure and the crystallinity increases according to the annealing time. 2-D nanoplate morphology is obtained for the sample that was annealed for 120 minutes. From the absorption spectra, it was found that the band gap decreases with increase of annealing time. Further, the prepared nanoparticle thin films are used as a cathode for photoelectrochemical water splitting application. Among these, the nanoparticles that are annealed for 120 minutes showed higher photocurrent density when compared to nanoparticles annealed for 60 minutes and 90 minutes.