Minimizing energy loss is a key aspect to transcend the current limitations on the performance of organic photovoltaics (OPV). However, an inherent limit has set for an organic bulk-heterojunction (BHJ) blends from prominent non-geminate recombination through non-radiative charge transfer states. Our recent study on charge recombination in BHJ and Planar-Mixed Heterojunction (PMHJ) blends comprising a donor with non-fullerene acceptors has shown both high photovoltaic internal quantum efficiency and high external electroluminescence quantum efficiency. Crystallographic and spectroscopic studies reveal that the fully-fused rigid molecular acceptors are not only intrinsically highly luminescent but also meets the criteria in achieving intrinsically radiative recombination within the blend, by promoting narrow distribution of charge transfer states with small structural reorganization. These results provide the important demonstration of radiative non-geminate charge recombination in an efficient OPV blend. In addition, the correlation between the photocarrier generation efficiency and the formation of recombined singlet/triplet charge transfer states that affects short-circuit current density in OPV is also identified. In this talk, the advances in molecular and process engineering of NFAs, and tuning of the corresponding polymer donor that enable significantly enhanced performance of OPV above 19% will be discussed. By integrating these highly efficient OPV with perovskite, stable organic/perovskite hybrid solar cells with PCE of >24% can also be achieved.