Exceptional power conversion efficiency (PCE) of 25.7% in perovskite solar cells (PSCs) has been achieved, which is comparable with their traditional rivals (Si‐based solar cells). However, commercialization‐worthy efficiency and long‐term stability remain a challenge. In this regard, there are increasing studies focusing on the interface engineering in PSC devices to overcome their poor technical readiness. Herein, the roles of electrode materials and interfaces in PSCs are discussed in terms of their PCEs and perovskite stability. All the current knowledge on the factors responsible for the rapid intrinsic and external degradation of PSCs is presented. Then, the roles of carbonaceous materials as substitutes for noble metals are focused on, along with the recent research progress in carbon‐based PSCs. Furthermore, a sub‐category of PSCs, that is, flexible PSCs, is considered as a type of exceptional power source due to their high power‐to‐weight ratios and figures of merit for next‐generation wearable electronics. Last, the future perspectives and directions for research in PSCs are discussed, with an emphasis on their commercialization. The roles of electrode materials and interfaces in perovskite solar cell (PSC) devices are discussed in terms of perovskite stability. The various factors responsible for rapid degradation in PSCs are provided. Then, the roles of carbonaceous materials for carbon‐based PSC as a substitute for noble metals are addressed, along with the recent progress.