Novel nanoflakes of Cu₂ZnSnS₄ (CZTS) thin film were directly deposited on fluorine doped tin oxide (FTO)-coated glass substrates by the successive ionic layer adsorption and reaction (SILAR) method. The results of energy dispersive X-ray spectroscopy (EDX) indicate that these CZTS thin films are Cu rich and S poor. The combination of X-ray diffraction (XRD results and Fourier Transform-Raman (FT-Raman) spectroscopy reveal that these thin films exhibit a strong preferential orientation of flakes along the [1 1 2] direction and that a small Cu_2−xS phase exists in CZTS thin films. Photoelectrochemical characterization revealed a p-type photo-response when the films were illuminated in an aqueous Eu³⁺ redox electrolyte. The total conversion power of the CZTS cell is 1.85% under 30 mW/cm² illumination.