Copper (1–5%)-doped tungsten oxide nanosheets has been synthesized using a solvothermal route for catalytic epoxidation of olefins to epoxides and hydrogen production. 5% Cu-WO3 (CW5) nanosheets is found to be highly efficient in selectively catalyzing olefins substrates (Styrene and Cyclohexene) to their corresponding epoxides with total conversion and better selectivity. CW5 nanosheets also exhibited highest photocatalytic activity with rate of hydrogen evolution of 2.69 mmol g−1 cat h−1 under visible light. It can also unveil outstanding performance as bi-functional water splitting electrocatalyst with 58 mA/cm2 current density at −1.2 V for HER and 1.58 mA/cm2 at an onset potential of 0.8 V for OER in alkaline medium.