The polymer/polymerBHJ solar cells achieved a PCE as high as 5.73%. The high performance was mainly attributed to the high charge carrier generation and collection efficiencies (80%) of PTB7–Th/N2200devices. To realize the full potential of N2200 as the polymeracceptor, quite a few works were carried out to develop appropriate polymer donors to match with N2200, thus to possess complementary absorption in the vis–NIR region, more balancedhole/electron mobilities, and better device performance.