Zinc(II) complexes of new macrocyclic tetraamines (cyclam derivatives) having a strategically appended phenolic group, 6-(2′-hydroxy)-benzyl-1,4,8,11-tetraazacyclotetradecane (L A), 6-(2′-hydroxy-5′-bromo)-benzyl-1,4,8,11- tetraazacyclotetradecane (L B) and 6-(2′-hydroxy-3′,5′-dibromo)-benzyl-1,4,8,11-tetraazacyclotetradecane (L C), have been examined as catalysts for the hydrolyses of 4-nitrophenylacetate (NA). The phenolic functionalized macrocycles from 1:1 ZnL complexes at pH ca 5. The potentiometric pH titration of L A, L B and L CZn II complexes showed dissociation of a phenolic proton with pKa values of 8,8, 8.7 and 8.5 at 298 K and I = 0.10 mol.l −1 KNO 3 for L A, L B and L CZn II complexes respectively. In the kinetic studies using the zinc complex in 10% (v/v) CH 3CN at 298 K, I = 0.10 mol.l −1 KNO 3 and pH 7.0–9.5, we proved that the coordinated phenolate can serve as a good nucleophile that effectively catalyzes NA hydrolysis. The hydrolysis rate follows the law v = ( k cat[complex]+ K OH[OH −]+ k 0[NA]. The pH rate profile gave a sigmoidal curve with inflection points at pH 8.8, 8.7 and 8.6 for L A, L B and L C, respectively, which correspond to the pKa value of the complex. The second-order (first-order each in complex and NA) rate constants are 0.056, 0.084 and 0.127 mol.l −1. s −1 for L A, L B and L C are obviously larger than the corresponding value of 0.047 mol.l −1. s −1 for N-methylcyclen-Zn(II)-OH − complex catalyst. This is, to our knowledge, the first phenolate coordinated zinc complex that efficiently catalyses the hydrolysis of 4-nitrophenyl acetate (NA). The present study also proves that solvolysis of NA ( i.e. water attack on the ester) does exist, but the reaction rate ( k 0 = 1.12 × 10 −5 s −1) is rather small.