ConspectusOrganic photovoltaics (OPVs), in which blend films of organic or polymer electron donor and electron acceptor are used as the active layer, are a promising photovoltaic technology with the great advantages of solution processing, low cost, and flexibility. The development of small molecular or polymer electron acceptors has boosted power conversion efficiency (PCE) of OPVs from 10% to 18%. Among them, polymer acceptors have the merits of superior morphology stability and excellent mechanical properties. However, owing to the key requirement of very low-lying LUMO/HOMO energy levels for polymer acceptors, very few conjugated polymers can work as polymer acceptors in OPVs. The majority of polymer electron acceptors are based on strong electron-withdrawing imide units or cyano substituents. Since 2015, conjugated polymers containing the boron-nitrogen coordination bond (B←N) have emerged as a new kind of polymer electron acceptor with excellent photovoltaic performance in various kinds of organic photovoltaic devices. In this Account, we summarize our research progress on polymer acceptors containing B←N units.At first, we introduce the principle of B←N to greatly down shift LUMO/HOMO energy levels, which enables B←N to be used to design polymer acceptors. Then we describe the two molecular design strategies for polymer acceptors containing B←N units. For high-efficiency OPVs, polymer acceptors should have wide absorption spectra, proper LUMO/HOMO energy levels, high electron mobility, and good donor/acceptor blend morphology. We discuss how to use molecular design to finely tune the absorption spectra, energy levels, and electron mobility of the B←N-containing polymer acceptors. We also discuss how to improve the phase separation morphology of the blends of these polymer acceptors with small molecular donors or polymer donors. These improvements lead to excellent performance of the polymer acceptors containing B←N units in three kinds of organic photovoltaic devices. The small molecular donor/polymer acceptor type organic solar cells show excellent thermal stability and PCE of 8.0%, which is the highest value reported so far. The all-polymer solar cells exhibit PCE of 10.1%. The all-polymer indoor photovoltaics show PCE as high as 27.4% under fluorescent lamp illumination at 2000 lx. This PCE is fairly comparable to those of the best organic or inorganic indoor photovoltaics. These results provide a solid foundation for future advances. Finally, we propose that great attention should be paid to further PCE enhancement of OPVs and indoor photovoltaic applications of this new emerging kind of polymer acceptor.