Photoactive bismuth vanadate (BiVO4) thin coatings were deposited on fluorine-doped tin oxide glass by plasma reactive sputtering from Bi2O3 and vanadium (V) radio frequency (RF) powered targets. The films were characterized by x-ray diffraction, scanning electron microscopy, energy dispersion spectroscopy, and UV-vis spectroscopy. The effects that the power density supplied to the Bi2O3 target, the post-annealing treatment, and the film thickness have on the structural features and on the photoelectrochemical (PEC) performances of the so obtained BiVO4 film-based photoelectrodes were investigated. Their PEC performance in water splitting was evaluated in a three-electrode cell by both incident photon to current efficiency (IPCE) and linear sweep voltammetry measurements under AM 1.5 G simulated solar light irradiation. A monoclinic phase of BiVO4, which is more photoactive than the tetragonal BiVO4 phase, was obtained by optimizing the power density supplied to the Bi2O3 target, i.e., by tuning the Bi:V:O atomic ratio. The best PEC performance was obtained for a stoichiometric 1:1 Bi:V atomic ratio, attained with 20 W power supplied at the Bi2O3 target and 300 W power supplied at the vanadium target, and an optimal 200 nm thickness of the BiVO4 film, with a 0.65 mA/cm2 photocurrent density attained at 1.23 V vs. standard calomel electrode, under simulated solar light. These results show the suitability of plasma reactive sputtering with two RF powered electrodes for the deposition of BiVO4 photoanodes for water splitting