The leakage and volatilization of liquid electrolytes limit the commercialization of dye-sensitized solar cells (DSCs). As solid-state (ss) hole-transporting materials, free from leakage and volatilization, biscarbazole-based polymers with different molecular weights (PBCzA-H (21,200 g/mol) and PBCzA-L (2450 g/mol)) were applied in combination with additives to produce ssDSCs. An ssDSC with PBCzA-H showed a better short-circuit current (J_sc), open-circuit voltage (V_oc), and fill factor (FF) than a device with PBCzA-L, resulting in 38% higher conversion efficiency. Compared to the PBCzA-L, the PBCzA-H with a higher molecular weight showed faster hole mobility and larger conductivity, leading to elevations in J_sc via rapid hole transport, V_oc via rapid hole extraction, and FF via lowered series and elevated shunt resistances. Thus, it is believed that PBCzA-H is a useful candidate for replacing liquid electrolytes.