A novel method for preparation of BiFeO3 films via a simple solution-based CVD method is reported using for the first time a single-source heterobimetallic precursor [CpFe(CO)2BiCl2]. BiFeO3 films display ferroelectric and ferromagnetic ordering at room temperature and possess direct band-gaps between 2.0 and 2.2 eV. Photocatalytic testing for water oxidation revealed high activities under UVA (365 nm) and simulated solar irradiation, superior to that exhibited by a commercial standard (Pilkington Activ® TiO2 film) resulting in an apparent quantum yield of ∼24%.