Layered perovskite Sr2TiO4 photocatalyst was synthesized by using sol-gel method with citric acid. In order to increase the surface area of layered perovskite Sr2TiO4, and thus to improve its photocatalytic activity for CO2 reduction, its surface was modified via hydrogen treatment or exfoliation. The physical and chemical properties of the prepared catalysts were characterized by X-ray diffraction, high-resolution transmission electron microscopy, elemental mapping analysis, energy-dispersive X-ray spectroscopy, N2 adsorption-desorption, UV-Vis spectroscopy, X-ray photoelectron spectroscopy, photoluminescence, and electrophoretic light scattering. CO2 photoreduction was performed in a closed reactor under 6 W/cm2 UV irradiation. The gaseous products were analyzed using a gas chromatograph equipped with flame ionization and thermal conductivity detectors. The exfoliated Sr2TiO4 catalyst (E-Sr2TiO4) exhibited a narrow band gap, a large surface area, and high dispersion. Owing to these advantageous properties, E-Sr2TiO4 photocatalyst showed an excellent catalytic performance for CO2 photoreduction reaction. The rate of CH4 production from the photoreduction of CO2 with H2O using E-Sr2TiO4 was about 3431.77 μmol/gcat after 8 h.