length region (the absorption peaks are located at 240 and 380 nm for [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) and PC 71 BM, respectively) and the deep lowest unoccupied molecular orbital (LUMO) energy levels (the LUMO energy levels are 4.1 eV and 3.9 eV for PCBM and PC 71 BM, respectively). [6,7] Fullerene-free acceptors have recently been vigorously developed and replaced the common fullerene derivative small molecule acceptor materials for high-performance OSCs, which play an important role in the broaden and redshifted absorption widows, and adjusting the LUMO and highest occupied molecular orbital (HOMO) energy levels. [8,9] However, a significant challenge of developed fullerene-free acceptors must be overcome in order to the absorption spectrum of fullerene free is match AM 1.5 G solar simulator and smooth energy levels at the donor/acceptor interface. Recently, the power conversion efficiencies (PCEs) of binary OSCs based on fullerenefree small molecular as acceptors (NFAs) have greatly developed. The single junction OSCs with Y6 as acceptor have led to PCE achieve 15.7% by Zou and co-workers reported. [10] The Peng et al. have reported the recorded PCE of single junction OSCs with Y6 as acceptor and achieved 16.35%. [11] The Erjun group has synthesized the new polymer PE2 and PE63 as donor and Y6 as acceptor and achieved the better photovoltaic performance. [12,13] At the same time, due to the LUMO and HOMO of third component materials located at the medium between donor and acceptor, it is evitable to introduce charge traps at the three kind materials interface. Thus, the third component materials should avoid to form deep charge traps, in addition to the large energy levels offset between HOMO of donor and LUMO of acceptor and complementary absorption peaks of photoactive layer materials. [14][15][16] Meta-alkyl-phenyl-containing 3,9-bis(2-methylene-(3-(1,1dicyanomethylene)-indanone))-5,5,11,11-tetrakis(4-hexyl phenyl)dithieno[2,3-d:2′,3′-d′]-s-indaceno[1,2-b:5,6-b′] dithiophene (ITIC) small molecular acceptor (m-ITIC) and alkylthienyl-containing ITIC small molecular acceptor (ITIC-Th) were reported. [17,18] The ITIC-Th exhibit the similar LUMO energy level (E LUMO , 3.85 eV) and significant downshifts of HOMO energy level (E HOMO , 5.66 eV) relative to m-ITIC (the E LUMO and E HOMO of 3.82 and 5.52 eV). Stimulatingly, the remarkable blueshifts absorption peaks for J61 polymer as donor and the blend of m-3,9-bis(2-methylene-(3-(1,1dicyanomethylene)-indanone))-5,5,11,11-tetrakis(4-hexyl phenyl)-dithieno[2,3d:2′,3′-d′]-s-indaceno[1,2-b:5,6-b′] dithiophene (ITIC) and ITIC-Th as electron acceptor. The blend of m-ITIC and ITIC-Th as electron acceptor due to the similar lowest unoccupied molecular orbital energy levels and good compatibility among J61, m-ITIC, and ITIC-Th, are beneficial for the small energy barrier at the m-ITIC:ITIC-Th interface. Simultaneously, the ternary photoactive layer can maintain the optimize film morphology and beneficial to ensure effective suppression of charge recombin...