HighlightsHighly performed perovskite solar cells are achieved via introducing organic–inorganic CL–NH complex as multifunctional interfacial layer.CL–NH complex not only reduces oxygen vacancies on the surface of SnO2but also regulates film crystallization, resulting in a superior device efficiency of 23.69%.The resulting device performs excellent stability with 91.5% initial power conversion efficiency retained after 500 h light illumination.Supplementary InformationThe online version contains supplementary material available at 10.1007/s40820-023-01130-5.