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 (Jsc), open-circuit voltage (Voc), 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 Jsc via rapid hole transport, Voc 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.