Hydrometallurgy has been increasingly used in the treatment of low-grade refractory ores owing to its relatively low energy consumption and cleaner process. Metal leaching is the primary step in hydrometallurgy, but there are still some acute problems such as low metal recovery rate and long reaction time. Chemical oxidation can transfer metal sulfides into metal ions or change the valence state of metals, and thus benefit the following separation and enrichment of the target metals. In this process, the metal leaching rate can also be further improved by external field enhancement. This review mainly describes the application and the main reaction mechanisms of five typical less corrosive chemical oxidants (Fe3+, O2, H2O2, O3 and persulfate), as well as the relevant collaborative oxidation methods in the hydrometallurgical processes, and introduces four strengthening methods by pressurization, special reaction medium, microwave and ultrasonic. Fe3+ is widely used in acidic leaching of chalcopyrite, sphalerite and other sulfide ores. The unique ion pair cycle enables Fe3+ to form a synergistic oxidation leaching mechanism with a variety of oxidants. O2 often enhances the oxidation leaching efficiency by pressure strengthening, which can promote the oxidative decomposition of refractory sulfide ores. H2O2 has attracted wide attention due to its strong oxidizing property and clean oxidation products, and has been widely used in electronic wastes treatment. O3 oxidation can help to effectively release wrapped gold into solution from refractory gold concentrate containing sulfur. Persulfate is relatively stable with strong oxidation ability, and can be activated to generate reactive oxygen species. Collaborative oxidation and four strengthening methods can further take the advantages of each oxidant to improve the oxidation effect and reduce the cost. Finally, the prospect and technical challenges of chemical oxidation strengthened hydrometallurgical technology are prospected, which has guiding significance for the development of clean production technology in hydrometallurgy.