Three‐coordinate Ph BOX Me2 ZnR ( Ph BOX Me2 = phenyl‐(4,4‐dimethyl‐oxazolinato; R = Me 2a , Et 2b ) catalyzes the dehydrocoupling of primary or secondary silanes and alcohols to give silyl ethers and hydrogen, with high turnover numbers (TON), up to 10 7 , under solvent‐free conditions. Primary and secondary silanes react with small, medium, and large alcohols to give varying degrees of substitution, from mono‐alkoxylation to tri‐alkoxylation, while tri‐substituted silanes do not react with MeOH under these conditions. The effect of coordinative unsaturation on the behavior of the Zn catalyst is revealed through a dramatic variation of both rate law and experimental rate constants, which depend on the concentrations of both the alcohol and silane reactants. That is, the catalyst adapts its mechanism access the most facile and efficient conversion. In particular, either alcohol or silane bind to the open coordination site on the Ph BOX Me2 ZnOR catalyst to form a Ph BOX Me2 ZnOR(HOR) complex under one set of conditions or an unprecedented σ‐adduct Ph BOX Me2 ZnOR(H–SiR' 3 ) under other conditions. Saturation kinetics provide evidence for the latter species, in support of the hypothesis that σ‐bond metathesis reactions, involving four‐centered electrocyclic 2σ‐2σ transition states, are preceded by σ‐adducts.