Perovskite-type lanthanum iron oxide, LaFeO3, is a promising photocathode material that can achieve water splitting under visible light. However, the performance of this photoelectrode material is limited by significant electron-hole recombination. In this work, we explore different strategies to optimize the activity of a nanostructured porous LaFeO3 film, which demonstrates enhanced photoelectrocatalytic activity due to the reduced diffusion length of the charge carriers. We found that surface passivation is not an efficient approach for enhancing the photoelectrochemical performance of LaFeO3, as it is sufficiently stable under photoelectrocatalytic conditions. Instead, the deposition of a Pt co-catalyst was shown to be essential for maximizing the photoelectrochemical activity both in hydrogen evolution and oxygen reduction reactions. Illumination-induced band edge unpinning was found to be a major challenge for the further development of LaFeO3 photocathodes for water-splitting applications.