Chemical vapor deposition (CVD) of UO2 thin films from in situ reductive decomposition using a U(VI) precursor ([U(OtBu)6]) was performed under applied magnetic fields (up to 1 T). The molecular mechanism responsible for the formation of U(IV) oxide was determined by nuclear magnetic resonance (NMR) analysis of gaseous byproducts revealed a reductive transformation of uranium hexakis-tert-butoxide into urania. Thin films were grown under zero-field and applied magnetic field conditions that clearly showed the guiding influence of the magnetic field on altering the morphology and crystallographic orientation of grains in UO2 deposits produced under an external magnetic field. Application of magnetic fields was found to reduce the grain size. Whereas films with a ⟨111⟩ preferred orientation were observed under zero-field conditions, the application of magnetic fields (500 mT to 1 T) promoted a polycrystalline growth. X-ray photoelectron spectroscopy confirmed the formation of UO2 films with traces of U(VI) centers present on the surface, which was evidently due to the surface oxidation of coordinatively unsaturated U(IV) centers, which was found to be significantly reduced in the field-assisted process. These findings emphasize the positive effect of magnetic fields on controlling the texture and chemical homogeneity of CVD-grown films. The availability of a magnetic field as an extrinsic parameter for the CVD process adds to the conventional parameters, such as temperature, deposition time, and pressure, and expands the experimental space for thin-film growth.