The photoinduced self-assembly and the formation of the mixed-valence state of tetrathiafulvalene (TTF) in the solid state are reported. The polymer composites containing TTF in poly(vinyl chloride) (PVC) were prepared, and oxidation of TTF by chlorine radical generated by UV irradiation in PVC was investigated. The formation of the mixed-valence state of TTF in the composite films by UV irradiation was observed, and the resulting TTF radical species, including the mixed-valence state after the photopatterning, exhibited extremely high stability in the composite films. Finally, we performed the fabrication of the gradient materials of the radical concentrations oil the TTF/PVC composites with the photopatterning.