An aza-crown ether ligand, 4,7,13,16-tetraethoxycarbonylmethyl-1,10-dioxa-4,7,13,16-tetraaza-18-C-6, was synthesized and characterized in this work. The binary complex containing cerium ion (III) and the ligand was determined by fluorescence technique and then used as catalyst in the hydrolysis of bis(4-nitrophenyl) phosphate ester (BNPP). The experimental data indicate that the cerium (III) complex exhibited higher catalytic activity than that of other catalytic systems in BNPP hydrolysis. Based on the experimental data, the intramolecular hydrolytic cleavage mechanism was proposed and the correlative thermodynamic and kinetic data were determined by the kinetic model established in this work.