Charged interfaces are key areas for charge transfer and chemical reactions. Studying these interfaces at the microscopic level, especially in constructing and characterizing specific structures, understanding charge transfer, and managing chemical reactions, is crucial but challenging. Our work focuses on three innovative interface structures: solid/solid triboelectric, liquid/gas electrified, and solid/ultrathin heterojunction interfaces. We have achieved significant insights into the charge transfer mechanisms within these electrified systems and effectively controlled catalytic reactions at these interfaces.Key findings include: Development of new concepts for contact electrification and electrostatic-induced coupling at solid/solid interfaces, leading to novel applications in energy conversion and catalysis. We introduced the concept of mechanical-electric-catalytic reactions based on triboelectric interfaces and achieved direct synthesis of hydrogen peroxide through friction-catalysis under normal conditions.Effective control of reaction kinetics and selectivity in charged microdroplet liquid/gas electrified interfaces by adjusting parameters like droplet evaporation rates and electric field characteristics. This approach led to efficient production of hydrogen peroxide and selective conversion of carbon dioxide.Precise atomic-level construction and sub-nanometer characterization of solid/ultrathin heterojunction interfaces, exemplified by gold/graphene interfaces. This included the development of a gold/ultrathin palladium/single-layer ruthenium structure, enabling in-depth study of hydroxylation reactions and the influence of palladium interlayers on ruthenium's catalytic efficiency.