The precise control of stoichiometric balance and ionic defects on the surface of solution-processed perovskite is critical to the performance and stability of perovskite solar cells (pero-SCs). Here, we introduce a low-cost and stable conjugated donor polymer (PTQ10) as interfacial layer in the planar n-i-p structured pero-SCs. The polymer was applied to the perovskite intermediate phase before the thermal annealing. This treatment significantly reduced the loss of surface organic cation during thermal annealing. Importantly, the kinetics of phase conversion of perovskite was influenced, and perovskite crystal showed a more preferential orientation. Moreover, the polymer proved to be an effective hole extraction layer due to the proper energy alignment with perovskite. Finally, a champion power conversion efficiency of the planar pero-SCs was achieved at 21.2% with a high fill factor of 81.6%. The devices also showed great ambient and thermal stability. This work presents a facile way of perovskite surface control to achieve high-performance pero-SCs.