Photocatalytic water splitting is one of the cleaner processes for molecular hydrogen and oxygen production using semiconductor. For better utilization of solar spectrum and complete redox for water splitting applications, it is required to have a semiconductor which is photoactive in visible region. The Bi2O3:Gd photocatalyst was successfully synthesized by Pechini method. The physical and chemical properties of as-prepared samples were characterized based on XRD, SEM, BET and UV-vis. Bi2O3 is an important inorganic functional material. It has got much attention due to its unique electrical and optical properties, which lead to its extensive usage in catalysis. Also, it is a promising visible-lightdriven photocatalyst whit a narrow bandgap (2.6-2.9 eV). It has been proved that β-Bi2O3 had the higher photocatalytic activity than α-Bi2O3 but only a few researches on β-Bi2O3 have been reported due to the difficulty of synthesizing the metastable β-phase [3]. The β-phase was confirmed using DRX.