The interaction between the metal and the support of supported metal catalysts, which are widely used in industry, is the primary focus of the study of such catalysts. With the developing understanding of the metal–support interaction, the intrinsic factor that influences the catalytic performance has been determined to be the structure of interfacial sites. Layered double hydroxides (LDHs, a class of two-dimensional layered anion clay) possess several unique characteristics, such as the follow-ing: (1) tunable elemental component, homogeneous distribution of metal cations. (2) anchoring eff ect. (3) multiple layered structure for exfoliation or intercalation and special memory eff ect; and (4) internal/external confinement eff ects during topological transformation. Taking LDHs and their derivatives as precursors or supports shows superior advantages in design-ing interfacial active catalysts with tunable properties. Therefore, this review is mainly focused on constructing interfacial active catalysts by LDHs and revealing the interfacial eff ects (including electronic, geometric, and bifunctional eff ects) on the catalytic performance that will provide new perspectives and approaches for the development of heterogeneous catalysis.