By looking global energy demands, development of highly efficient stable semiconductor photoelectrodes for photoelectrochemical (PEC) water splitting is highly desirable. Herein, we have fabricated co-catalytic nanoparticles decorated Silicon nanowire (SiNWs)/Hematite(Fe2O3) core sell structures as photo anodes and studied the PEC water oxidation properties. As, Fe2O3 possess weak oxidation kinetics, decoration of NiO and Co3O4 nanoparticles on SiNW/Fe2O3 by hydrothermal method, which acts as co-catalysts to improves the water oxidation reactions. It was found that decoration of Co3O4 nanoparticles enhances the photocurrent up to 2.6 times, whereas for NiO nanoparticles improvement is of 1.5 times when compared to the undecorated electrodes. Along with enhancement of photocurrents, it also shows shift of onset potentials. The effect of the co-catalytic nanoparticles on the enhancement of photocurrent and charge transfer resistance at the interface of electrode-electrolyte have been studied by electrochemical impedance spectroscopy. Further, flat band potentials of the photo electrodes have been measured by using Mott-schottky analysis.