jats:titleAbstract</jats:title>jats:pPerovskite semiconductors are an attractive option to overcome the limitations of established silicon based photovoltaic (PV) technologies due to their exceptional opto‐electronic properties and their successful integration into multijunction cells. However, the performance of single‐ and multijunction cells is largely limited by significant nonradiative recombination at the perovskite/organic electron transport layer junctions. In this work, the cause of interfacial recombination at the perovskite/Cjats:sub60</jats:sub> interface is revealed via a combination of photoluminescence, photoelectron spectroscopy, and first‐principle numerical simulations. It is found that the most significant contribution to the total Cjats:sub60</jats:sub>‐induced recombination loss occurs within the first monolayer of Cjats:sub60</jats:sub>, rather than in the bulk of Cjats:sub60</jats:sub> or at the perovskite surface. The experiments show that the Cjats:sub60</jats:sub> molecules act as deep trap states when in direct contact with the perovskite. It is further demonstrated that by reducing the surface coverage of Cjats:sub60</jats:sub>, the radiative efficiency of the bare perovskite layer can be retained. The findings of this work pave the way toward overcoming one of the most critical remaining performance losses in perovskite solar cells.</jats:p>