InTaO4 is an efficient visible-light photocatalyst, which used to be synthesized by solid-state fusion at over 1100 °C. However, irregular morphology and severe agglomeration of particles were acquired due to nonuniform fusion of solid precursors. In this study, InTaO4 was synthesized by two sol-gel routes, the thermal hydrolysis and esterification methods. The precursors were indium (III) nitrate pentahydrate [In(NO3)3] and tantalum(V) butoxide [Ta(OC4H9)5] dissolved in solutions. The InTaO4 powders with a uniform grain size of 17.7 nm were successfully synthesized using the esterification method at a calcination temperature of 950 °C. A uniform InTaO4 thin film nearly 40 nm thick formed on an optical fiber at 1100 °C using the sol prepared by the esterification method. For the first time, InTaO4 was evaluated by the photocatalytic activity of CO2 photo reduction, which was conducted in aqueous solution under visible light irradiation. Cocatalyst NiO was loaded on the surface of InTaO4 to further enhance the methanol yield. The methanol yields of NiO/InTaO4 by esterification method were significantly higher than those by solid-state fusion. The esterification method provided homogeneous mixing of Ta(OC4H9)5 and In(NO3)3, resulting in nano-sized InTaO4 with uniform crystallinity and superior photocatalytic activity.