Core-shell structured co-catalyst has been created much attention in photocatalytic hydrogen production due to their efficient electron-hole pair separation, suppression of surface back reaction and long term stability. Here, we report the preparation of CuO@NiO hierarchical nanostructures as a co-catalyst deposited on TiO2 nanospheres for enhanced photocatalytic hydrogen generation. The formation of ultrathin NiO shell over the CuO core was confirmed by TEM analysis. Fabricated core-shell nano structured CuO@NiO over TiO2 nanospheres was studied for hydrogen evolution under the direct solar light and it showed a high rate of H-2 production of 26.1 mmol. h(-1). g(cat)(-1). It was scrutinized that the rate of hydrogen production was improved with shell thickness and co-catalyst loading. Systematic investigation on CuO@NiO co-catalyst loading, pH of the medium and glycerol concentration for augmented H-2 production. The recorded rate of hydrogen production is almost six folds greater than that of pristine TiO2. In the view of largescale synthesis for alternative energy storage applications, the composited photocatalyst was made of by simple mixing method, which could be scaled up without any loss in photocatalytic activity. Further, the stability test of photocatalyst for continuous use found that 82% of initial photocatalytic activity is retained even after three days. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.