Reliable and predictable catalytic reactions that produce either regioisomer when starting from the same raw materials, also called regiodivergent reaction methodologies, are highly desirable. The different regioisomers can be prepared by properly interchanging the catalysts or altering the reaction conditions. Therefore, these regiodivergent reactions exhibit higher productivity, better atom-and step-economy, and better cost-efficiency and are quickly gaining favour in synthetic organic chemistry. As was summarized by Nájera and coworkers, different catalysts, ligands, solvents, or additives, were the predominant strategy for the implementation of regiodivergent features in metal-catalysed organic synthesis. The achievement of switchable selectivity using quickly and conveniently controlled physical variables constitutes a desirable goal with an intriguing method of attainment. Reaction temperature, one of the most easily changed physical variables in organic synthesis, can affect the regioselectivity of reactions (Figure ). For example, the Kolbe-Schmitt reaction, the named reaction for the synthesis of salicylic acid, is a thermodynamically controlled equilibrium reaction. A lower reaction temperature is conducive to the formation of ortho-isomers, and a higher reaction temperature is conducive to the formation of para-isomers. Fries rearrangement reaction also exhibits a temperature-regulated regiodivergence. In another example, Martin and coworkers reported the discovery of a temperature-dependent regiodivergent remote carboxylation of alkyl halides with carbon dioxide. The site-specific formation of carbon-carbon or carbon-heteroatom bonds provides new insight to chemists during retrosynthetic analysis. Alkene (migratory) functionalization represents an attractive method for the construction of carbon-carbon bonds and carbon-heteroatom bonds. The in situ generation of alkyl-metallic intermediates from widely accessible alkenes circumvents the time-consuming use of reactive and often sensitive organometallic reagents in traditional electrophile-nucleophile cross-coupling, which improves our everexpanding synthetic toolkit for forming sp 3 hybridized linkages. In addition, carbon-carbon bond formation on remote and unfunctionalized sites enabled by the chain-walking process, a formal translocation of the original active site to a nonspecific position along with the carbon skeletons, allows for the synthesis of complex structures that would otherwise be difficult to prepare. In the context of alkene functionalization, both catalysts and ligands could regulate the regiodivergence of hydrofunctionalization and difunctionalization process . In consideration of the essential problem that to achieve switchable selectivity using easily changed and controlled physical variables, switching reaction temperatures to provide the regiodivergent products starting from a single alkene substrate would be an ideal choice.