Abstract.The main aim of this study was to investigate the effect of deposition time on the physicochemical and photoelectrochemical properties of cupric oxide (CuO) thin films synthesized via electrodeposition method. Firstly, the electrodeposition of amorphous CuO films on fluorine-doped tin oxide (FTO) working electrodes with varying deposition time between 5 and 30 min was carried out, followed by annealing treatment at 500 ℃. Resultant nanocrystalline CuO thin films were characterised using field emission-scanning electron microscopy (FE-SEM), photocurrent density, and photoluminescence measurements. Through FE-SEM analysis, it was observed that the surface of thin films was composed of irregular-sized CuO nanocrystals. A smaller CuO nanocrystals size will lead to a higher photoactivity due to the increase in overall catalytic surface area. In addition, the smaller CuO nanocrystals size will prolongs the electron-hole recombination rate due to the increase in copious amount of surface defects. From this study, it was revealed that the relationship between deposition time and CuO film thickness was non-linear. This could be due to the detachment of CuO thin films from the FTO surface at an increasing amount of CuO mass being deposited. It was observed that the amount of light absorbed by CuO thin films increased with film thickness until a certain extent whereby, any further increase in the film thickness will result in a reduction of light photon penetration. Therefore, the CuO nanocrystals size and film thickness have to be compromised in order to yield a higher catalytic surface area and a lower rate of surface charge recombination. Finally, it was found that the deposition time of 15 min resulted in an average CuO nanocrystals size of 73.7 nm, optimum film thickness of 0.73 μm, and corresponding photocurrent density of 0.23 mA/cm 2 at the potential bias of -0.3 V (versus Ag/AgCl). The PL spectra for the deposition time of 15 min has the lowest rate of recombination of photogenerated electron-hole pairs by referring to its lowest PL intensity.