We present a combined light-induced electron paramagnetic resonance (LEPR) study of photoinitiation, relaxation, and recombination of charge carriers initiated by achromatic/white (with a color temperature of 5000 K) and monochromatic (with a photon energy of 1.34–3.41 eV) light in PBDB-T-based photovoltaic systems with PC₆₁BM, PC₇₁BM, and ITIC-M counterions. Charge carriers, polarons on polymer chains, and respective radical anions excited in disordered composite matrixes first fill spin traps, the number, energy depth, and spatial distribution of which are determined by the structure and crystallinity of bulk heterojunctions. By deconvolution of the effective LEPR spectra, the contributions of immobilized and mobile charge carriers, as well as their main magnetic resonance parameters, were determined separately at a wide variety of experimental conditions. The interaction of spins occupying different energy levels in the bandgap of a polymer semiconductor provokes the extreme photon energy sensitivity of the spin-assisted processes carried out in the polymer composites. The density functional theory calculations of the millimeter-waveband LEPR spectrum allowed the conclusion that polarons photoinitiated in the PBDB-T backbone are delocalized over its 4–5 monomers. Side π–π-stack packaging and S-isomerization of electron acceptors were also found. Predominant nongeminate recombination of charge carriers follows multistep trapping–detrapping spin hopping between sites of polymer layers and is strongly governed by the number, energy depth, and spatial distribution of spin traps. It was shown that all spin-involving processes in composites are spin-assisted and, therefore, are determined by the main magnetic resonance properties of both the spin charge carriers. The stability of charge carriers in a polymer-based composite was demonstrated to increase by more than an order of magnitude in the series of radical anions PC₆₁BM^–• → ITIC-M^–• → PC₇₁BM^–•. A further improvement in the functionality of the composite occurs at its slight 2,5-diphenyloxazole modification. The use of low-dimensional ITIC-M instead of PCBM and/or PPO with extended π-system significantly increases the exchange interaction between the spin charge carriers situated on the adjacent layers of the composite. This blocks intrachain charge diffusion but accelerates its interlayer hopping in the polymer matrix, which increases the efficiency and functionality of the composite.