The present invention provides an acrylate polymer capillary electrochromatography column decorated by macrocyclic polyamine and its preparing method, the column of acrylate polymer organic polymer decorated by macrocyclic polyamine is prepared by free radical polymerization and method of column back decoration, the whole surface of the acrylate polymer in the electrochromatography column is linked with a macrocyclic polyamine, the macrocyclic polyamine is 1, 4, 10, 13, 16-quinquevalent nitrogen trinuclear heneicosane-9, 17-diketone. The preparing method of acrylate polymer capillary electrochromatography column decorated by macrocyclic polyamine is simple, having better reproduction quality, the capillary electrochromatography column has a better separating effect to inorganic anions, benzenediol isomer, benzoic acid derivatives and ribonucleotide, having better application in the separating aspect for complicated component material.