Highly donor-doped (110) layered perovskite materials, La2Ti2O7, with high surface areas were synthesized by the polymerizable complex (PC) method. Relative to La2Ti2O7 prepared by the solid state reaction (SSR) method, PC catalysts showed higher surface areas, crystallization at lower temperatures, higher phase purity, more uniform morphology and better-distributed nickel on the outer surface of La2Ti2O7. All these factors led to higher photocatalytic activity for overall water splitting under UV irradiation. The quantum yield of the reaction over La2Ti2O7 prepared by the PC method was as high as 27%, which was about twofold greater than that over La2Ti2O7 prepared by the SSR method.