We present a theoretical investigation on various semiconducting materials that exhibit photovoltaic and photoluminecent properties. Our focus is on the relaxation dynamics that occur upon photoexcitation of a couple of type II donor-acceptor heterojunction systems. In addition to the diabatic approach our two-band exciton model employs to study the phonon-assisted relaxations, we adopt the Marcus-Hush semiclassical method to incorporate lattice reorganization. This enables us to look at the state-to-state interconversions from the relaxed excited-state configurations in model polymer blends of poly( 9,9-dioctylfluorene-co-N-(4-butylphenyl) diphenylamine) (TFB) with poly(9,9-dioctylfluorene-co-benzothiadiazole) (F8BT) and poly(9,9-dioctylfluorene-co-bis-N,N-(4-butylphenyl)-bis-N,N-phenyl-1,4-p henylenediamine) (PFB) with F8BT. Our results stress the significance of vibrational relaxation in the state-to-state relaxation. Furthermore, while a tightly bound charge-transfer state (exciplex) remains the lowest excited state, we show that the regeneration of the optically active lowest excitonic state in TFB: F8BT is possible via the existence of a steady state.