The incorporation of potassium into perovskite solar cells (PSCs) has been empirically validated to mitigate hysteresis phenomena and boost the power conversion efficiency (PCE). However, the doping mechanism of potassium ions in the perovskite film and their effect on photocarrier recombination remains a topic of debate. Here, we grew doped MAPbI3: K single crystals by inverse temperature crystallization using KI as a dopant, and then perovskite thin films were spin-coated with dissolved MAPbI3: K crystals as a precursor. The doped MAPbI3: K perovskite films exhibit better crystal quality with large columnar grains and lower defect density. Employing Hall effect, ultraviolet photoelectron spectroscopy, and Kelvin probe force microscopy measurements, we definitively demonstrate that K-doping transforms the conductivity type of the perovskite film from a marginally N-type to a distinct P-type semiconductor. Furthermore, this doping strategy induces a concurrent downward shift in both the conduction band minimum and valence band maximum. As a result, the PCE of the PSCs increases from 15.15% to an impressive 20.66%, and the J–V curve hysteresis almost disappears. Additionally, theoretical simulations using SCAPS-1D software reveal a profound modification in the device's energy band diagram after K+-doping. Specifically, the energy level offset between the perovskite layer and the electron transport layer diminishes from 0.24 to 0.14 eV, with a result of bigger quasi-Fermi energy level splitting. This, in turn, elevates the open-circuit voltage (Voc) of the doped perovskite solar cell, underscoring the profound impact of potassium doping on enhancing PSC performance.