To incorporate new functionalities, various oxide materials can be composited with metal nanoparticles to form metal–oxide nanostructures, which are very promising for a wide range of applications. In this review, we summarize the recent developments in advanced synthesis of structure-diversified core–shell, yolk–shell, Janus, and their combined metal–oxide nanostructures. We also summarize their representative catalytic applications including organic reduction and oxidation, CO oxidation, CO2 conversion, water–gas shift reaction, and water splitting. We discuss recyclable metal–oxide nanocatalysts with mesoporous, hollow, or multilayered structures. We highlight perspectives for their challenges ahead and opportunities for their widely used applications in plasmon localization enhanced photocatalysis, artificial enzyme catalysis, and catalytic biomass conversion.