During the past five years, polymer solar cells (PSCs) based on narrow bandgap (NBG) fused-ring small molecule (SM) acceptors have made considerable progress, [1][2][3][4] among which the state-of-the-art PSCs have achieved power conversion efficiencies (PCEs) of 16-18%. [5][6][7][8][9][10][11][12][13][14][15][16][17] Regarding such SM acceptor-based PSCs, the all-polymer solar cells (all-PSCs) consisting of a polymer donor and a polymer acceptor show unique advantages in the flexible large-scale and wearable energy generators due to their excellent morphology stability and mechanical robustness. [18][19][20][21] However, most of the efficient all-PSCs have PCEs ranging in 8-10%, [22][23][24][25][26][27][28][29][30][31][32][33][34] although a few of them achieved PCEs over 11%, [35][36][37] which is still far behind that of the efficient PSCs based on SM acceptors due to the lack of high-performance polymer acceptors. To date, polymer acceptors have been mainly confined into a small number of structural building blocks, [24][25][26][38][39][40] and the most widely studied one is the polymer N2200 with a donor-acceptor (D-A) backbone of naphthalene diimide (NDI)-alt-bithiophene due to its NBG and suitable molecular energy levels. [39][40][41][42][43] However, N2200 neat film suffers from a low absorption coefficient of %0.3 Â 10 5 cm À1 and an excess strong crystallinity and stacking, which usually lead to the limited photocurrent and large phase separation in active layers. [39][40][41][42][43] The limited light absorption capacity for most polymer acceptors hinders the improvement of the power conversion efficiency (PCE) of all-polymer solar cells (all-PSCs). Herein, by simultaneously increasing the conjugation of the acceptor unit and enhancing the electron-donating ability of the donor unit, a novel narrowbandgap polymer acceptor PF3-DTCO based on an A-D-A-structured acceptor unit ITIC16 and a carbon-oxygen (C-O)-bridged donor unit DTCO is developed. The extended conjugation of the acceptor units from IDIC16 to ITIC16 results in a red-shifted absorption spectrum and improved absorption coefficient without significant reduction of the lowest unoccupied molecular orbital energy level. Moreover, in addition to further broadening the absorption spectrum by the enhanced intramolecular charge transfer effect, the introduction of C-O bridges into the donor unit improves the absorption coefficient and electron mobility, as well as optimizes the morphology and molecular order of active layers. As a result, the PF3-DTCO achieves a higher PCE of 10.13% with a higher short-circuit current density ( J sc ) of 15.75 mA cm À2 in all-PSCs compared with its original polymer acceptor PF2-DTC (PCE ¼ 8.95% and J sc ¼ 13.82 mA cm À2 ). Herein, a promising method is provided to construct high-performance polymer acceptors with excellent optical absorption for efficient all-PSCs.