Photocatalytic hydrogen (H2) production by water splitting provides an alternative to fossil fuels using clean and renewable energy, which gives important requirements about the efficiency of photocatalysts, co-catalysts, and sacrificial agents. To achieve higher H2 production efficiencies from water splitting, the study uses different metals such as yttrium (Y), praseodymium (Pr), magnesium (Mg), Indium (In), calcium (Ca), europium (Eu), and terbium (Tb) doped lanthanum iron oxide (LaFeO3) perovskites. They were synthesized using a co-precipitate method in a citric acid solution, which was loaded with the rhodium chromium oxide (RhCrOx) cocatalysts by an impregnation method along with a detailed investigation of photocatalytic hydrogen evolution performance. Photoluminescence (PL) and UV–Vis diffuse reflectance spectra (DRS) measured the rate of electron–hole recombination for RhCrOx/Pr-LaFeO3 photocatalysts, and X-ray powder diffraction (XRD), scanning electron microscope (SEM), high resolution transmission electron microscope (HRTEM), and X-ray photoelectron spectra (XPS) analyzed their characteristics. The experimental results obtained show that the samples with 0.5 wt.% RhCrOx loading and 0.1 M Pr-doped LaFeO3 calcined at a temperature of 700 °C (0.1Pr-LaFeO3-700) exhibited the highest photocatalytic H2 evolution rate of 127 µmol h−1 g−1, which is 34% higher photocatalytic H2 evolution performance than undoped LaFeO3 photocatalysts (94.8 μmol h−1 g−1). A measure of 20% of triethanolamine (TEOA) enabled a high hole capture capability and promoted 0.1-Pr-LaFeO3-700 to get the highest H2 evolution rate. [ABSTRACT FROM AUTHOR]