Tetrabenzoporphyrin (BP) holds attractive characteristics for optoelectronic applications, such as the large π-conjugated framework and high photoabsorption capability. However, its use in organic solar cells (OSCs) has been limited because of the extremely low solubility that hampers direct solution processing and also the high frontier-orbital energies that lead to low open-circuit voltage (VOC). Herein, we examine BP derivatives equipped with multiple strongly electron-withdrawing groups for photovoltaic applications. The derivatives are generated in thin films through a thermal precursor approach, wherein the corresponding bicyclo[2.2.2]octadiene-fused porphyrin derivatives are solution-cast, and then annealed to carry out the in situ retro-Diels-Alder reaction. The frontier-orbital energies of the resulting derivatives are effectively stabilized as compared to pristine BP to such a degree that they afford high VOC of up to 0.94 V when used as a donor or can even work as a new class of nonfullerene acceptor in OSCs. Single-crystal X-ray diffraction analyses demonstrate that the conformation of the BP framework largely varies from being near planar to highly curved depending on its substituents. The morphology of polymer:BP-derivative bulk-heterojunction films prepared by the thermal precursor approach also varies between the BP derivatives. These results can greatly extend the scope of both molecular design and morphology control for utilization of the BP chromophore toward achieving viable organic optoelectronic devices.