Interfacial ligand passivation engineering has recently been recognized as a promising avenue, contributing simultaneously to the optoelectronic characteristics and moisture/operation tolerance of perovskite solar cells. To further achieve a win-win situation of both performance and stability, an innovative conjugated aniline modifier (3-phenyl-2-propen-1-amine; PPEA) is explored to moderately tailor organolead halide perovskites films. Here, the conjugated PPEA presents both “quasi-coplanar” rigid geometrical configuration and distinct electron delocalization characteristics. After a moderate treatment, a stronger dipole capping layer can be formed at the perovskite/transporting interface to achieve favorable banding alignment, thus enlarging the built-in potential and promoting charge extraction. Meanwhile, a conjugated cation coordinated to the surface of the perovskite grains/units can form preferably ordered overlapping, not only passivating the surface defects but also providing a fast path for charge exchange. Benefiting from this, a ≈21% efficiency of the PPEA-modified solar cell can be obtained, accompanied by long-term stability (maintaining 90.2% of initial power conversion efficiency after 1000 h testing, 25 °C, and 40 ± 10 humidity). This innovative conjugated molecule “bridge” can also perform on a larger scale, with a performance of 18.43% at an area of 1.96 cm2.