Although direct arylation polymerization (DArP) has recently emerged as an alternative to traditional cross-coupling methods like Suzuki polymerization, the evaluation of DArP polymers in practical applications like polymer solar cells (PSCs) is limited. Because even the presence of minute quantities of defects can dramatically influence the solar cell, performance of DArP polymers offers critical insight alongside other structural and optoelectronic comparisons. Even via traditional methods, carbazole-based donors are frequently prone to homocoupling defects, which has been shown to—along with β-defects—compromise performance. Through defect minimization with the bulky and affordable neodecanoic acid (NDA) mixture, we report the synthesis of DArP poly[(9-(heptadecan-9-yl)-9H-carbazole)-alt-(4,7-di(thiophen-2-yl)benzo[c][1,2,5]thiadiazole)] (PCDTBT) that outperforms Suzuki PCDTBT with similar molecular weights. Expanding beyond this model system, carbazole-based polymers featuring 2,5-diethylhexyl-3,6-di(thiophen-2-yl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione (DPP), 4,10-bis(diethylhexyl)-thieno[2′,3′:5,6]pyrido[3,4-g]thieno[3,2-c]isoquinoline-5,11-dione (TPTI), 5-octyl-1,3-di(thiophen-2-yl)-4H-thieno[3,4-c]pyrrole-4,6(5H)-dione (DT-TPD), and 2,5-bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)pyridine (EDOT-Pyr) are generated. Polymers are characterized by ¹H NMR, cyclic voltammetry, UV-Vis, GIXRD, SCLC hole mobilities, and are implemented into polymer solar cells fabricated in air under ambient humidity. We demonstrate that DArP polymers perform comparably to Suzuki in practical applications.