The invention discloses zinc, magnesium and calcium complexes of monophenol ligands with similar salan-structures as well as a preparation method thereof and the application in lactone ring-opening polymerization. The preparation method comprises the steps as follows: the similar salan-monophenol ligands react with zinc, magnesium and calcium metallo-organic compounds, and then target products are collected from reaction coarse products. The zinc, magnesium and calcium complexes comprise asymmetrical multidentate amino monophenol oxygroup ligands with the similar salan-structures, are effective lactone ring-opening polymerization catalysts, and can be used for ring-opening polymerization of lactide, caprolactone and the like. The multidentate monophenol oxygroup zinc, magnesium and calcium complexes have the very obvious advantages as follows: raw materials are easy to get, the synthetic route is simple, separation and purification are easy, and the performance is stable relatively; meanwhile, high catalytic activity is achieved; in addition, polylactone that is obtained through catalysis has higher molecular weight, and the requirements of industrial sectors can be satisfied. The structure of the zinc, magnesium and calcium complexes has the following general formula.