Abstract: | Carbon electrode are a low‐cost and great potential strategy for stable perovskite solar cells (PSCs). However, the efficiency of carbon‐based PSCs lags far behind compared with that of state‐of‐the‐art PSCs. The poor interface contact between the carbon electrode and the underlying layer dominates the performance loss of the reported carbon‐based PSCs. In this respect, a sort of self‐adhesive macroporous carbon film is developed as counter electrode by a room‐temperature solvent‐exchange method. Via a simple press transfer technique, the carbon film can form excellent interface contact with the underlying hole transporting layer, remarkably beneficial to interface charge transfer. A power conversion efficiency of up to 19.2% is obtained for mesoporous‐structure PSCs, which is the best achieved for carbon‐based PSCs. Moreover, the device exhibits greatly improved long‐term stability. It retains over 95% of the initial efficiency after 1000 h storage under ambient atmosphere. Furthermore, after aging for 80 h under illumination and maximum power point in nitrogen atmosphere, the carbon‐based PSC retains over 94% of its initial performance. |