Biopolymer films derived from starch and chitosan were soaked in vanadium salt solutions to produce vanadium metallopolymer films. Visible light irradiation induces significant color shifts from yellow to green due to changes in the oxidation state of vanadium. The material was observed to undergo dramatic structural changes upon incorporation of vanadium, with further restructuring occurring after visible light illumination. Metallopolymer films exhibited enhanced hydrophobic properties, which were further amplified when the material was irradiated with visible light, resulting in water contact angles up to 103°. X-ray photoelectron spectroscopy (XPS) measurements reveal that photoirradiation reduces vanadium metal from the 5+ (VO