Photo-electrochemical properties of fluorine-doped tin oxide (FTO)/nickel oxide-nickel (Ni0.98Si0.02O2-Ni) with isolated Si sites are discussed. The Ni0.98Si0.02O2-Ni photo-electrocatalyst without any noble metal was prepared using a one-step chemical reduction precipitation method. Photo-electrochemical properties were investigated by cyclic voltammetry and chronoamperometry techniques in aqueous alkaline solution at pH 8.0. The photo-electrochemical response of the catalyst showed sensitivity to visible and UV light. The catalyst produced hydrogen from water at a rate of 0.5 mmol g(-1) h(-1) with the reduction of CO2 into CO under visible light in the absence of any light sensitizer or a noble metal. The metallic Ni amount in the catalyst system was optimized to obtain the best photo-electrocatalyst. The first principle DFT study showed that the incorporation of Si sites allowed absorbance of visible light. The catalyst was characterized by powder x-ray diffraction (PXRD), scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS), inductively coupled plasma- atomic emission spectroscopy (ICP-AES), Brunauer-Emmett-Teller (BET), cyclic voltammetry, and chronoamperometry. The products were analyzed by gas chromatography- thermal conductivity detector (GC-TCD). [GRAPHICS] .