AbstractThe fullerene C₆₀ is commonly applied as the electron transport layer in high‐efficiency metal halide perovskite solar cells and has been found to limit their open circuit voltage. Through ultra‐sensitive near‐UV photoelectron spectroscopy in constant final state mode (CFSYS), with an unusually high probing depth of 5–10 nm, the perovskite/C₆₀ interface energetics and defect formation is investigated. It is demonstrated how to consistently determine the energy level alignment by CFSYS and avoid misinterpretations by accounting for the measurement‐induced surface photovoltage in photoactive layer stacks. The energetic offset between the perovskite valence band maximum and the C₆₀ HOMO‐edge is directly determined to be 0.55 eV. Furthermore, the voltage enhancement upon the incorporation of a LiF interlayer at the interface can be attributed to originate from a mild dipole effect and probably the presence of fixed charges, both reducing the hole concentration in the vicinity of the perovskite/C₆₀ interface. This yields a field effect passivation, which overcompensates the observed enhanced defect density in the first monolayers of C₆₀.