The novel synthesis method of phenol type benzo-15-crown-5 ether resin was proposed. The chemical bonding of benzo-crown ether and phenol was succeeded by using hexamethylenetetramine and trichloroacetic acid as the condensing agent and solvent, respectively. The control of the diameter and shape of resin was also succeeded by using the high porous silica beads support. The isotope fractionation by chromatography using the synthesized resin was confirmed. The lighter isotope was disproportionately located in the crown ether resin. The separation coefficient, ", in the present system was 0.033.