Tetracoordinate silicon species are typically tetrahedral, weak Lewis acids, and often sensitive to moisture. In this study, we present a tetra-amido macrocyclic ligand (TAML)-substituted Si(IV), isolated as its bis(pyridine) adduct. Due to structural constraint toward anti van’t-Hof/Le Bel geometry, this compound exhibits Lewis superacidity and effectively catalyzes the hydroboration of pyridine. Kinetic and computational analyses of the catalytic cycle reveal that TAML-Si(IV) acts as a …