Numerous homogeneous catalyst-initiator systems are known and utilized in industrial scale to conduct various autoxidation processes. The reaction mechanism and kinetic details of homogeneous liquid phase autoxidation have been extensively investigated. This article presents an overview on the state of the art of heterogeneous catalyst-initiator systems in the liquid phase oxidation of hydrocarbons. Mechanistic insights and limitations of the heterogeneous catalyst-initiator systems are discussed. The potentials and challenges towards an industrial application are evaluated.