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In this article, we designed and synthesized a novel small molecule acceptor of ITCPTC with thiophene-fused ending group by employing a new active methylene precursor of CPTCN. The ITCPTC based polymer solar cells with PBT1-EH as donor achieved very high PCEs of up to 11.8% with a remarkably enhanced fill factor (FF) of 0.751, a near 20% boost in PCE with respect to the ITIC based control device. These values are among the highest PCEs and FFs for PSCs. In the whole study, we made contrasts with ITIC to understand the reasons of excellent performance of ITCPTC-based PSCs through various measurements, such as GIWAXS and RSoXS. We revealed that the simple modification of ITIC into ITCPTC not only change the material electronic structure, but also mediate the material interactions and crystallization, which contribute together to the excellent performance of ITCPTC based PSCs., Comment: 23 pages; Corrected a typo on page 23