A series of novel polymers (P1P6) derived from the combination of different units (including thiophene, triarylamine, and spirobifluorene) were successfully synthesized, completely characterized, and used as hole-transporting materials (HTMs) for perovskite solar cells (PSCs). Solar cells with some of these materials as HTMs showed very good performances of almost 13% (12.75% for P4 and 12.38% for P6) even without additives, and devices based on these new HTMs show relatively improved stability against temperature compared to those based on PTAA. The presence of dopant additives has been linked to long-term degradation, which is the main barrier to the large-scale commercialization of this innovative type of solar cell. Obtaining efficient PSCs without using dopants could represent a further step toward improvement of long-term stability and thus their introduction into the market.