We report on multi layered ZnCdO photoanode structures synthesized on c-A1 2 O 3 substrates using metal organic vapor phase epitaxy and covered with a thin TiO 2 protective film using atomic layer deposition and pulsed laser deposition techniques. Structural, optical and photoelectrochemical properties of the multilayers were investigated systematically in connection with their potential application in the photolysis of water. X-ray diffraction and Rutherford backscattering techniques confirmed staggered arrangement and graded Cd content of the multilayers. Temperature-dependant photoluminescence revealed excitonic nature of a broad emission band representing combined band-edge emissions from the individual layers. The photocurrent was found to increase with decreasing thickness of the TiO 2 protective layer.