This study focuses on enhancing the photoelectro - catalytic (PEC) performance of LaFeO₃ photocathodes by incorporating Ag nanocrystals. LaFeO₃, a perovskite - type metal oxide semiconductor, has potential in PEC water splitting but suffers from fast charge carrier recombination. Ag nanoparticles are introduced due to their surface plasmon resonance (SPR) property and ability to form Schottky junctions with LaFeO₃. A series of Ag/LaFeO₃ materials are prepared using the molten salt method for LaFeO₃ synthesis and the direct reduction method for Ag loading. The results show that Ag nanoparticles are uniformly dispersed on LaFeO₃. The 3 mol% Ag loading significantly enhances the photocurrent density, about 9 - fold higher than that of pure LaFeO₃. Ag loading improves light absorption, reduces the band gap, and optimizes charge kinetics. EIS and Mott - Schottky analysis reveal that 3 mol% Ag/LaFeO₃ has the lowest charge transfer impedance and the highest carrier concentration. This work provides valuable insights into the interaction between Ag and LaFeO₃, and offers experimental and theoretical support for developing efficient photocatalytic materials for PEC water splitting.