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In this work, one novel asymmetric non-fullerene acceptor ITIC-3T was designed and synthesized. ITIC-3T molecule shows 1.58 eV E g , with −3.95 eV LUMO level. Utilizing P3 (one asymmetric 2D conjugated benzodithiophene polymer) as donor material, bulk heterojunction solar cells were fabricated. The optimal device yields a PCE of 6.47% with a V OC of 0.64 V, a FF of 55.5% and a high J SC of 18.18 mA cm−2, which may be attributed to the complementary optical absorption of active blend (P3 and ITIC-3T). In general, this work demonstrates that asymmetric polymer donor and non-fullerene acceptor active layer blend is potential for fabricating efficient photovoltaic cells. Image 1 • Novel asymmetric A-D-A type non-fullerene acceptor ITIC-3T was synthesized and firstly reported. • Solar cell device based on asymmetric BDT-based polymer and asymmetric non-fullerene acceptor shows PCE of 6.47%. • Extraordinary J SC was achieved based on asymmetric polymer donor and non-fullerene acceptor device of 18.18 mA cm−2. [ABSTRACT FROM AUTHOR]