Direct arylation polymerization (DArP) has emerged as a greener and more atom-efficient alternative to Stille polymerization. Despite the attractiveness of this method, DArP is known to produce β-linkages in polymers, which have β-protons available for activation. Here, we report the influence of the β-defect content in DArP poly(3-hexylthiophene) (P3HT) on the performance of bulk-heterojunction solar cells and the morphology of pristine polymers and their blends with PC61BM in thin films and compare with Stille P3HT containing 0% β-defects as a reference point. The optical and electrochemical properties as well as the hole mobilities of pristine polymers remain virtually the same when the amount of β-defects is limited to 0.75% or lower, as evidenced by UV-visible absorption spectra, cyclic voltammetry and space-charge-limited current (SCLC) mobility measurements. However, an increase of β-defect concentration to 1.41% significantly affects the oxidation onset, UV-visible absorption profile and hole mobility of P3HT. The key result of this study is that the photovoltaic performance of DArP P3HT with 0% β-defects is remarkably close to that of Stille P3HT, whereas the performance of DArP P3HT with 0-0.75% β-defects does not differ dramatically from that of Stille P3HT and could potentially be improved upon by individual optimization of the processing conditions.