Rationally designing interface structure to modulate the electronic structure of a photocatalyst is an efficient strategy to facilitate the separation and migration of photogenerated charge carriers and improve photocatalytic activity. In this work, a AgCl/Pd heterostructure encapsulated by N‐doped carbon nanotubes (AgCl/Pd@N−C) with a fan‐like morphology assembled hollow tubes was synthesized by pyrolysis of a AgCl/Pd@Bim precursor. The unique interface structure not only increases the number of photogenerated charge carriers, but also provides an effective channel for the separation of electrons and holes, which have been proved by density functional theory (DFT) calculations. As expected, the obtained AgCl/Pd‐3@N−C exhibited greatly enhanced conversion efficiency and recyclability toward the photocatalytic oxidative coupling of amine under blue‐light irradiation.