Polyoxometalate-intercalated layered double hydroxide (POM-LDH) nanocomposites have received considerable attention in recent years because such nanocomposites not only inherit the intrinsic properties of POMs and LDHs but also exert significant synergistic effects during the catalytic process. In this frontier article, we present the latest advances on the POM-LDH nanocomposites ranging from new synthetic methods to catalytic applications. By making use of the host layer modification method and exfoliation assembly method, the as-prepared POM-LDH nanocomposites show a wide range of catalytic applications. The challenges and future opportunities are also discussed by highlighting some creative work on related POM- or LDH-based materials. Polyoxometalates-intercalated layered double hydroxides (POMs-LDHs) nanocomposites have received considerable attention recently owing to the intrinsic properties of POMs and LDHs and significant synergistic effects during the catalytic process.