The secret to the success of mixed bulk heterojunctions (BHJs) in yielding highly efficient organic solar cells (OSCs) could reside in the molecular structures at their donor/acceptor (D/A) interfaces. In this study, we aimed to determine the effects of energy and charge cascade structures at the interfaces by using well-defined planar heterojunctions (PHJs) as a model system. The results showed that (1) the charge cascade structure enhanced VOC because it shuts down the recombination pathway through charge transfer (CT) state with a low energy, (2) the charge cascade layer having a wider energy gap than the bulk material decreased JSC because the diffusion of the excitons from the bulk to D/A interface was blocked; the energy of the cascade layers must be appropriately arranged for both the charges and the excitons, and (3) molecular intermixing in the cascade layer opened the recombination path through the low-energy CT state and decreased VOC. Based on these findings, we propose improved structures for D/A interfaces in BHJs.