A new p-type photocathode LaFeO3 was successfully fabricated, and a stable (120 h) and effective water splitting (H2: 11.5 μmol h(-1), O2: 5.7 μmol h(-1)) was realized via construction of a p-LaFeO3/n-Fe2O3 photocell. This study offers a new alternative to p-type photocathode materials and the low cost design of durable PEC devices for solar conversion.