Direct arylation polycondensation (DArP) is an emerging synthetic method of producing conjugated polymers in an environmentally benign and cost-effective manner. We now report the synthesis of hole-transporting conjugated polymers, namely, DPP-OMe (Mn = 7.9 kg/mol) and DPP-F (Mn = 12.6 kg/mol), under microwave-assisted DArP conditions. These two polymers and the previously synthesized 3,6-Cbz-EDOT were evaluated as hole-transporting materials in mesoscopic perovskite solar cells. 3,6-Cbz-EDOT synthesized by DArP exhibited higher hole mobility and better photovoltaic properties than that synthesized by the Stille polycondensation. Moreover, chemical dopants improved the short-circuit current density (Jsc) and fill factor.