Improving efficiency and stability has become an urgent issue in the application of perovskite solar cells (PSCs). Herein, a kind of long‐chain polymer or polymethylmethacrylate (PMMA) is added into the spiro‐OMeTAD matrix to improve the film formation process and hence the device performance. It is observed that, after modification, the spiro‐OMeTAD‐based hole‐transporting layer becomes uniform, continuous, and condensed. Meanwhile, the power conversion efficiency of the devices is upgraded. Compared with the control device, open‐circuit voltage of the modified one (with moderate doping) increases from 1.06 (±0.03) to 1.10 (±0.02) V, fill factor increases from 72.20 (±3.44)% to 75.59 (±3.35)%, and the power conversion efficiency increases from 18.82 (±1.06)% to 20.51 (±0.82)% (highest at 21.78%) under standard test condition (AM 1.5G, 100 mW cm−2). Transient photocurrent/photovoltage decay curves, time‐resolved photoluminance, and impedance spectroscopy studies show that the modification could accelerate charge transfer and retard interfacial recombination. In addition, the modification improves device stability. Due to the strengthened barrier against penetration of “H2O/O2/Ag,” the efficiency of the unsealed device could retain 91.49% (by average) of the initial one after 100 days storage in the dark [relative humidity = 30(±5)%]. This work shows that long‐chain polymer doping could simultaneously improve efficiency and stability of spiro‐OMeTAD‐based PSCs.