We designed a stable and efficient CuO based photocathode by tuning the crystallinity and surface morphology of films by rapid thermal treatment. The role of the annealing temperature on film crystallinity, optical absorption and grain size is studied. The impact of these parameters upon the photocatalytic water splitting performance of CuO films is investigated. We observed that a higher annealing temperature improves the film crystallinity and increases the grain size of CuO film, which significantly enhance the photocurrent generation capability. Rapid thermal annealing at 550 °C is found the best temperature to achieve the highest PEC performance. The thickness of the CuO photocathodes is also optimized and we observed that 550 nm thick films results in the highest photocurrent of 1.68 mA cm⁻². Our optimized CuO photocathode has shown better stability against photo-corrosion and a 30% decrease in the initial value of photocurrent is measured after 15 min, while a 60% decrease in the photocurrent is noticed in case of the as-deposited film.