ABSTRACT: Two wide band-gap copolymers poly[4,8-bis(5-(2-butylhexylthio)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene-2,6-diyl-alt-TZNT] (PBDTS-TZNT) and poly[4,8-bis(4-fluoro-5-(2-butylhexylthio)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene-2,6-diyl-alt-TZNT] (PBDTSF-TZNT) based on naphtho[1,2-c:5,6-c]bis(2-octyl-[1,2,3]triazole) (TZNT) and benzo[1,2-b:4,5-b']dithiophene (BDT) with different conjugated side chains have been developed for efficient nonfullerene polymer solar cells (NF-PSCs). The rigid planar backbone of BDT and TZNT units imparted high crystallinity and good molecular stacking property to these copolymers. Using 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone)-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3-d:2',3'-d']-s-indaceno[1,2-b:5,6-b']-dithiophene (ITIC) as the acceptor, PBDTSF-TZNT devices showed a high Voc of 0.98 V with an Eloss of 0.61 eV. On selecting 3,9-bis(2-methylene-(5,6-difluoro-(3-(1,1-dicyanomethylene)-indanone)-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3-d:2',3'-d']-s-indaceno[1,2-b:5,6-b']-dithiophene (IT-4F) instead of ITIC, the devices maintained the high Voc of 0.93 V with an even lower Eloss of 0.59 eV. The combination of the above-mentioned low Eloss, broadened absorption, better matched energy level, improved crystallinity, and fine-tuned morphology promoted the power conversion efficiency (PCE) of PBDTSF-TZNT:IT-4F devices from 12.16% to 13.25%. Homo-tandem devices based on PBDTSF-TZNT:IT-4F subcells further enhanced the light-harvesting ability and boosted the PCE of 14.52%, which is the best value for homo-tandem NF-PSCs at present.