Charge resonance and charge transfer interactions of dicyanovinylstyrylpyridinyl radicals were observed at room temperature in organic solvents by steady photolysis with absorption and ESR spectroscopy, Excitation of dicyanovinylstyrylpyridinium salts with tetraphenylborate in less polar solvents resulted in photoinduced electron transfer reactions to form fairly stable dicyanovinylstyrylpyridinyl radicals. In addition to the remarkable color changes due to the characteristic absorption of dicyanovinylstyrylpyridinyl radicals in the visible region, a charge resonance absorption band (CR band) of dimer radical cations and a charge transfer band of radical dimers were observed in the neat-infrared region with peaks at 1050 and 1120 nm, respectively. The rise of the CR band was observed in the pulse width of a nanosecond laser, which was as fast as that of the formation of radical itself.