With effectively improved spectral resolution and signal-to-noise ratio, PL features are well resolved in the Te- and Cd-rich CdZnTe crystals and ascribed to the neutral donor-bound exciton (DX), acceptor-bound exciton (AX), A-center, and deep donor–acceptor pair. A detailed analysis indicates that (i) Cd pressure annealing drives the Te inclusions to the surface region of the crystal, destroys the inclusions by excess Cd atoms, and releases abundant donor-like and acceptor-like impurities; (ii) the PL features of the deep energy levels at 1.30–1.55 eV originate in the A-center consisting Cd vacancy and one type shallow donor, and the PL feature at 1.474 eV is the so-called SA luminescence of a donor–acceptor transition between an A-center and another shallow donor. A quantitative description of the recombination scheme is established, and by which the effects of the annealing are clarified.