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We report the synthesis and characterization of two diastereomeric phosphoramidite calix[4]pyrrole cavitands and their corresponding gold(I) complexes, 2 in •Au(I)•Cl and 2 out •Au(I)•Cl, featuring the metal center directed inward and outward with respect to their aromatic cavity. We studied the catalytic activity of the complexes in the hydration of a series of propargyl esters as the benchmarking reaction. All substrates were equipped with a six-membered ring substituent either lacking or including a polar group featuring different hydrogen bond acceptor (HBA) capabilities. We designed the substrates with the polar group to form 1:1 inclusion complexes of different stabilities with the catalysts. In the case of 2 in •Au(I)•OTf, the 1:1 complex placed the alkynyl group of the bound substrate close to the metal center. We compared the obtained results with those of a model phosphoramidite gold(I) complex lacking a calix[4]pyrrole cavity. We found that for all catalysts, the presence of an increasingly polar HBA group in the substrate provoked a decrease in the hydration rate constants. We attributed this result to the competing coordination of the HBA group of the substrate for the Au(I) metal center of the catalysts.