Benzylic carboxylates and carbonates react with various molecules in the presence of homogeneous palladium or cobalt catalysts. The catalytic transformations occur at the benzylic carbons of the substrates, affording benzylic substitution products. This review surveys the catalytic reactions using benzylic carboxylates and carbonates as substrates. Furthermore, the related studies on (η³-benzyl)metal complexes are summarized in order to facilitate the understanding and consideration of the catalytic substitution. 1 Introduction 2 Chemistry of the (η³-Benzyl)metal Complex 2.1 Structure of the (η³-Benzyl)metal Complex 2.2 Reactivity of the (η³-Benzyl)metal Complex 3 Catalytic Transformations of Benzylic Esters 3.1 Nucleophilic Substitution 3.2 Cross-Coupling with Organometallic Compounds 3.3 Miscellaneous Reactions 4 Concluding Remarks