AbstractPerovskite solar cells have demonstrated low non‐radiative voltage losses and open‐circuit voltages (V_OCs) that often match the internal voltage in the perovskite layer, i.e. the quasi‐Femi level splitting (QFLS). However, in many cases, the V_OC differs remarkably from the internal voltage, for example in devices without perfect energy alignment. In terms of recombination losses, this loss often outweighs all non‐radiative recombination losses observed in photoluminescence quantum efficiency measurements by many orders of magnitude. As such, understanding this phenomenon is of great importance for further perovskite solar cell development and tackling stability issues. The classical theory developed for Si solar cells explains the QFLS‐V_OC mismatch by considering the partial resistances/conductivities for majority and minority carriers. Here, the authors demonstrate that this generic theory applies to a variety of physical mechanisms that give rise to such a mismatch. Additionally, it is found that mobile ions can contribute to a QFLS‐V_OC mismatch in realistic perovskite cells, and it is demonstrated that this can explain various key observations about light soaking and aging‐induced V_OC losses. The findings in this paper shine a light on well‐debated topics in the community, identify a new degradation loss, and highlight important design principles to maximize the V_OC for improved perovskite solar cells.