Single phase magnesium ferrite films (MgFe2O4) were grown by magnetic field-assisted chemical vapor deposition (CVD) of mixed-metal precursor [MgFe2(OtBu)8] with metal ratio corresponding to the spinel stoichiometry (Mg: Fe = 1:2). Thin film deposition was performed in a CVD reactor equipped with external magnets, which allowed to investigate film growth as a function of the applied field strength (B = 0.0, 0.5 and 1.0 T). The formation of monophasic MgFe2O4 deposits was confirmed by X-ray diffraction, and photoelectron spectroscopy. The cross-sectional analysis (FIB-SEM) of the film revealed an increased densification and crystal growth, upon application of the magnetic field when compared to zero-field deposition. The MgFe2O4 films deposited under zero-field and field-assisted conditions were used as electrodes in a photoelectrochemical (PEC) water-splitting reaction. All the three samples showed a stable performance and photocurrent values, however the photocurrent was found to gradually decrease with increasing applied magnetic field (0 T: 5.74 µA/cm2, 0.5 T 2.33 µA/cm2 and 1 T: 1.33 µA/cm2 at 1.23 V), which is possibly due to change in absorption properties and crystal orientation, decreasing photoabsorption intensity provided by the UV-vis results and the latter being evident in the disappearance of (220) peak in MgFe2O4 films grown under the influence of external magnetic field .