Defects at the surface and grain boundaries of metal–halide perovskite films lead to performance losses of perovskite solar cells (PSCs). Here, organic cyano‐based π‐conjugated molecules composed of indacenodithieno[3,2‐b]thiophene (IDTT) are reported and it is found that their cyano group can effectively passivate such defects. To achieve a homogeneous distribution, these molecules are dissolved in the antisolvent, used to initiate the perovskite crystallization. It is found that these molecules are self‐anchored at the grain boundaries due to their strong binding to undercoordinated Pb2+. On a device level, this passivation scheme enhances the charge separation and transport at the grain boundaries due to the well‐matched energetic levels between the passivant and the perovskite. Consequently, these benefits contribute directly to the achievement of power conversion efficiencies as high as 21.2%, as well as the improved environmental and thermal stability of the PSCs. The surface treatment provides a new strategy to simultaneously passivate defects and enhance charge extraction/transport at the device interface by manipulating the anchoring groups of the molecules.