Four manganese(III) complexes (MnL 1 Cl, MnL 2 Cl, MnL 4 2 Cl, MnL 5 2 Cl) with a crowned salicylaldimine Schiff base ligand have been synthesized and employed as models to mimic hydrolase in the hydrolysis of p-nitrophenyl picolinate (PNPP). The kinetics and mechanism of catalytic PNPP hydrolysis have been investigated. The kinetic mathematical model of PNPP cleavage catalyzed by these complexes has been proposed. The effects of the ligand structure and crown ether ring in complexes, and the reactive temperature on the rate of catalytic PNPP hydrolysis have been also examined. The results show that compared with the crown-free analogous MnL 3 Cl and MnL 6 2 Cl, the crowned Schiff base manganese(III) complexes, MnL 1 Cl, MnL 2 Cl, MnL 4 2 Cl and MnL 5 2 Cl, exhibit more high catalytic activity, which follow the order: MnL 1 Cl >MnL 2 Cl >MnL 4 2 Cl >MnL 5 2 Cl >MnL 3 Cl >MnL 6 2 Cl; the pseudo-first-order-rate (k obs ) for the PNPP hydrolysis catalyzed by the complex MnL 1 Cl containing three crown ether rings is highest among six complexes and is 1.81 times that of MnL 3 Cl, 1.49 · 10 3 times that of spontaneous hydrolysis of PNPP, respectively, at pH = 7.00, [S] = 2.0 · 10 )4 mol dm )3 .