The dynamic competition between electron generation and recombination was found to be a bottleneck restricting the development of high-performance dye-sensitized solar cells (DSSCs). Introducing a passivation layer on the surface of the TiO2 photoelectrode material plays a crucial role in separating the charge by preventing the recombination of photogenerated electrons with the oxidized species. This study aims to understand in detail the kinetics of the electron recombination process of a DSSC fabricated with a conductive substrate and photoelectrode film, both passivized with a layer of nanocrystalline TiO2. Interestingly, the coating, which acted as a passivation layer, suppressed the back-electron transfer and improved the overall performance of the integrated DSSC. The passivation layer reduced the exposed site of the fluorine-doped tin oxide (FTO)-electrolyte interface, thereby reducing the dark current phenomenon. In addition, the presence of the passivation layer reduced the rate of electron recombination related to the surface state recombination, as well as the trapping/de-trapping phenomenon. The photovoltaic properties of the nanocrystalline-coated DSSC, such as short-circuit current, open-circuit voltage, and fill factor, showed significant improvement compared to the un-coated photoelectrode film. The overall performance efficiency improved by about 22 compared to the un-coated photoelectrode-based DSSC. © 2020 by the authors.