Bulk-heterojunction (BHJ) molecular blends prepared from small molecules based on diketopyrrolopyrrole (DPP) and perylene-diimide (PDI) chromophores have been studied using optical absorption, cyclic voltammetry, photoluminescence quenching, X-ray diffraction, atomic force microscopy, and current-voltage measurements. The results provided useful insights into the use of DPP and PDI based molecules as donor-acceptor composites for organic photovoltaic (OPV) applications. Beside optoelectronic compatibility, the choice of active layer processing conditions is of key importance to improve the performance of BHJ solar cells. In this context, post-production treatments, viz. thermal and solvent vapour annealing, and the use of 1,8-diiodooctane as a solvent additive were employed to optimize the morphology of blend films. X-ray diffraction and atomic force microscopy indicated that the aforementioned processing strategies led to non-optimal composite morphologies with significantly large crystallites in comparison to exciton diffusion lengths. Although the open circuit voltage of the OPV devices was satisfactory (0.78 V), it was anticipated that the bulky domains hamper charge dissociation and transport, which resulted in low photovoltaic performance.