Magnetic, relaxation, and dynamic parameters of radical pairs of positively charged polarons and negatively charged anion radicals of fullerene that are induced by photons with an energy of 1.7–3.4 eV are studied by the methods of photoinduced electron paramagnetic resonance for the poly(3hexylthiophene)–fullerene composite. The above charge carriers show mutual independence, which is provided by a different interaction with their microenvironment. The paramagnetic susceptibility of spin pairs reflects the dipole–dipole interaction and activation dynamics of paramagnetic sites in the polymer–fullerene system. The rate of recombination of radical pairs is controlled by the mutual space distribution of carriers of various charges and by the energy of excitation photons. Quasionedimensional diffusion of polarons along polymer chains and rotational diffusion of fullerene molecules about the selected molecular axis are likewise controlled by the energy of photons and can be described in terms of the activation Elliott hopping model. The dependence of the main values of magnetic, relaxation, and dynamic parameters of charge carriers on the energy of photons is explained by the inhomogeneous distribution of molecular clusters in the polymer–fullerene composite. The annealing of this composite leads to an enhanced formation of polymer crystallites and fullerene clusters. Hence, the effective dimension of the system increases and its electron characteristics are improved.