Charge carriers photoinduced in poly(3-dodecylthiophene)/([6,6]-phenyl-C61-butanoic acid methyl ester) (P3DDT/PCBM) by photons with the energy of 1.88–2.75 eV were investigated by X-band light-induced electron paramagnetic resonance (LEPR). LEPR spectra were attributed to non-interacting polarons and methanofullerene anion radicals with different magnetic and relaxation parameters. A part of these charge carriers are trapped in a polymer matrix. Paramagnetic susceptibility and spin–spin relaxation of mobile charge carriers were shown to follow the activation law. Charge carriers photoinduced in poly(3-dodecylthiophene)/([6,6]-phenyl-C61-butanoic acid methyl ester) (P3DDT/PCBM) by photons with the energy of 1.88–2.75 eV were investigated by X-band light-induced electron paramagnetic resonance (LEPR). LEPR spectra were attributed to non-interacting polarons and methanofullerene anion radicals with different magnetic and relaxation parameters. A part of these charge carriers are trapped in a polymer matrix. Paramagnetic susceptibility and spin–spin relaxation of mobile charge carriers were shown to follow the activation law.