The kinetics of the behavior of photosensitive impurities and defects in the high-purity semi-insulating material 4H-SiC has been studied both theoretically and experimentally using electron paramagnetic resonance (EPR) under photoexcitation and optical admittance spectroscopy. The rate equations describing the processes of recombination, trapping, and ionization of nonequilibrium charge carriers bound dynamically to shallow donors and acceptors (nitrogen and boron), as well as of charge carrier transfer from the shallow nitrogen donor to deep levels of intrinsic defects, have been solved. A comparison of the calculations with the experimental curves plotting the decay of admittance conductance and EPR signal intensities due to nitrogen and boron after termination of photoexcitation has revealed that the probabilities of hole trapping by an ionized acceptor and the rate of ionization of a neutral boron acceptor are two orders of magnitude higher than those of similar processes in a system of donor levels. The latter is dominated by cascade electron transitions between levels in the band gap, as well as by electron–hole recombination