Nanocrystalline Bi2Se3-Sb2Se3 multilayer thin films were deposited by simple and less investigated successive ionic layer adsorption and reaction (SILAR) method onto glass- and fluorine-doped tin oxide (FTO)-coated glass substrate from aqueous solution. Characterizations such as XRD, surface morphology and optical absorption have been carried out for Bi2Se3-Sb2Se3 thin films onto glass substrates. The films deposited onto FTO-coated glass substrates were used to study photoelectrochemical behaviour in 0.1M (NaOH-Na2S-S) electrolyte and results are reported.