Metal halide perovskite single crystals are promising for diverse optoelectronic applications due to their outstanding properties. In comparison to the bulk, the crystal surface suffers from high defect density and is moisture sensitive; however, surface modification strategies of perovskite single crystals are relatively deficient. Herein, solar cells based on methylammonium lead triiodide (MAPbI3) thin single crystals are selected as a prototype to improve single‐crystal perovskite devices by surface modification. The surface trap passivation and protection against moisture of MAPbI3 thin single crystals are achieved by one bifunctional molecule 3‐mercaptopropyl(dimethoxy)methylsilane (MDMS). The sulfur atom of MDMS can coordinate with bare Pb2+ of MAPbI3 single crystals to reduce surface defect density and nonradiative recombination. As a result, the modified devices show a remarkable efficiency of 22.2%, which is the highest value for single‐crystal MAPbI3 solar cells. Moreover, MDMS modification mitigates surface ion migration, leading to enhanced reverse‐bias stability. Finally, the cross‐link of silane molecules forms a protective layer on the crystal surface, which results in enhanced moisture stability of both materials and devices. This work provides an effective way for surface modification of perovskite single crystals, which is important for improving the performance of single‐crystal perovskite solar cells, photodetectors, X‐ray detectors, etc.

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