The catalytic oxidation of primary alcohols to carboxyl compounds is an extremely important transformation process in organic synthesis, with a wide range of application scenarios. For heterogeneous catalytic oxidation systems, the preparation of efficient catalysts has always been a hot and difficult research topic. This article provides a comprehensive review of recent literature on the preparation of carboxyl compounds by heterogeneous catalytic oxidation of primary alcohols. The development status and trends of heterogeneous catalysts for the oxidation of primary alcohols were systematically evaluated in terms of single metal and bimetallic active components, as well as the utilization of supports. Furthermore, the prospects and challenges of heterogeneous catalysis in industrial applications were discussed.