A new benzodithiophene(BDT)-alt-fluorobenzotriazole(FBTA) D-A copolymer J40 was designed and synthesized by introducing 2-octyldodecyloxy side chains on its BDT units, for expanding the family of the BDT- alt-FBTA-based copolymers and investigating the side chain effect on the photovoltaic performance of the polymer in non-fullerene polymer solar cells(PSCs).J40 exhibits complementary absorption spectra and matched electronic energy levels with the n-type organic semiconductor(n-OS)(3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3-d:2′,3′-d′]-sindaceno[1,2-b:5,6-b′]dithiophene)(ITIC) acceptor, and was used as polymer donor in the non-fullerene PSCs with ITIC as acceptor. The power conversion efficiency(PCE) of the PSCs based on J40:ITIC(1:1, w/w) with thermal annealing at 120 °C for 10 min reached 6.48% with a higher open-circuit voltage(Voc) of 0.89 V. The high Voc of the PSCs is benefitted from the lower-lying highest occupied molecular orbital(HOMO) energy level of J40. Although the photovoltaic performance of the polymer J40 with alkoxy side chain is lower than that of J60 and J61 with alkylthio-thienyl conjugated side chains, the PCE of6.48% for the J40-based device is still a relatively higher photovoltaic efficiency in the non-fullerene PSCs reported so far. The results indicate that the family of the BDT-alt-FBTA-based D-A copolymers are high performance polymer donor materials for non-fullerene PSCs and the side chain engineering plays an important role in the design of high performance polymer donors in the non-fullerene PSCs. A new benzodithiophene (BDT) -alt-fluorobenzotriazole (FBTA) DA copolymer J40 was designed and synthesized by introducing 2-octyldodecyloxy side chains on its BDT units, for expanding the family of the BDT-alt-FBTA-based copolymers and investigating the side chain effect on the photovoltaic performance of the polymer in non-fullerene polymer solar cells (PSCs). J40 exhibits complementary absorption spectra and matched electronic energy levels with the n-type organic semiconductor (n-OS) (3,9-bis -methylene- (3- (1,1-dicyanomethylene) -indanone) -5,5,11,11-tetrakis (4-hexylphenyl) -dithieno [2,3- d: 2 ’, 3’-d’ -indaceno [1,2-b: 5,6-b ’] dithiophene (ITIC) acceptor, and was used as polymer donor in the non-fullerene PSCs with ITIC as acceptor. The power conversion efficiency (PCE) of the PSCs based on J40: ITIC (1: 1, w / w) with thermal annealing at 120 ° C for 10 min reached 6.48% with a higher open circuit voltage (Voc) of 0.89 V. The high Voc of the PSCs is benefitted from the lower-lying highest oc cupped molecular orbital (HOMO) energy level of J40. Although the photovoltaic performance of the polymer J40 with alkoxy side chain is lower than that of J60 and J61 with alkylthio-thienyl conjugated side chains, the PCE of 6.48% for the J40-based device is still a relatively higher photovoltaic efficiency in the non-fullerene PSCs reported so far. The results indicate that the family of the BDT-alt-FBTA-based DA copolymers are high performance polymer donor materials for non-fullerene PSCs and the side chain engineering plays an important role in the design of high performance polymer donors in the non-fullerene PSCs.