Triarylsilanols have been employed as the first silicon-based molecular catalysts for direct amidation of carboxylic acids. Tris(p-bromophenyl)silanol exhibited superior catalytic activity amongst tris(p-haloaryl)silanols selected for this study. Kinetic experiments revealed that Lewis acidic arylsilanol catalysts are sensitive to product inhibition, thus explaining the observed diminished catalytic efficiency in direct amidation reactions investigated. Tertiary amides proved to be more detrimental to the catalytic activity than secondary amides in the event of product inhibition. Accelerated catalyst deactivation in the presence of more basic secondary amines was evidenced by ex situ HPLC catalyst quantification. Computational studies uncovered the likelihood of a pentacoordinate silyl ester-amide complex as the possible mode of catalyst inhibition.