Mullite-type Bi2Fe4O9 has been little explored in thin film form as a photoanode for photoelectrochemical water splitting. In this study, Bi2Fe4O9 thin films have been prepared using the sol-gel technique from a simple precursor solution based on the corresponding metal salts, acetic acid, and polyvinyl alcohol. The films were deposited by dip-coating onto fluorine-doped tin oxide substrates and dried at 350 °C, repeating the dipping-drying cycle six times, and finally sintered at 600 °C. The films were characterized by GIXRD, revealing the formation of the material in its orthorhombic phase. Raman spectroscopy showed the Ag and B1g vibrational modes, validating the formation of the bismuth iron oxide. UV–Vis transmittance measurements revealed that the material exhibits two optical transitions: a direct band gap of 2.86 eV and an indirect band gap of 1.98 eV. FESEM micrographs and AFM images showed a uniform nanostructured surface morphology. The photoelectrochemical properties of the Bi2Fe4O9 films were studied using cyclic voltammetry and chronoamperometry with front side illumination, demonstrating the stability of the material in aqueous media and the generation of photocurrent in the presence of H2O2. Furthermore, results from intensity-modulated photocurrent spectroscopy (IMPS) revealed that the photocurrent is limited by both bulk and surface recombination and a short hole diffusion length.