Metal nanowires coated with multilayer films of (TiO2/W12O41)(3)(PAN/SWNT)(3)PAN (12 nm thick; PAN: Polyaniline; SWNT: single-walled carbon nanotube) are synthesized using different, templated, layer-by-layer assembly techniques. Their I-V characteristics indicate a built-in p-n junction at the TiO2/PAN interface (rectification ratio >120 at 3 V). Films grown on planar substrates have similar thickness, morphology, and electrical properties.