We present a comprehensive study, combining experimental and theoretical approaches, to assess the hydrogen evolution reaction (HER) efficiency of BiFeO₃-based solid solutions. Initially, we investigate the electronic and optical properties of these compounds, with a particular focus on band edge alignment relative to water redox potentials. Our findings show that the materials exhibit optimal band gaps of approximately 2.0 eV, indicative of enhanced visible light absorption and favorable energetic alignment to drive efficient hydrogen generation. To corroborate our theoretical predictions, we perform photoelectrochemical measurements on selected BiFeO₃-based compounds synthesized via the solid-state method. Our experimental results reveal a high hydrogen yield, with BiFeO₃-SrTiO₃ achieving a production rate of ∼114 µmol/L in 30 min, outperforming BiFeO₃-BaTiO₃ (∼70 µmol/L) and pristine BiFeO₃ (∼61 µmol/L). These findings validate our theoretical assumptions and demonstrate the superior HER performance of BiFeO₃-SrTiO₃, positioning it as a highly promising candidate for sustainable hydrogen production.