Silylenes, the silicon analogues of carbenes, have emerged as an important class of divalent silicon compounds. Through strategic kinetic and thermodynamic stabilization, numerous isolable cyclic and acyclic silylenes have been developed, serving as effective ligands in transition metal chemistry. This chapter presents a comprehensive overview of the synthesis, structural features, and catalytic applications of silylene-transition metal complexes. It highlights the significant potential of these complexes in catalysis and small-molecule activation.