Synthesis of a vinyl monomer, containing a 32-membered crown ether unit (VCE) as a pendant group, was achieved by using tetra(ethylene glycol) dichloride, resorcinol, and 3,5-dihydroxyacetophenone as starting materials. The product was identified by means of FTIR and H-1-NMR. It was found that this monomer readily polymerizes by the conventional radical initiator 2,2'-azobisisobutyronitrile (AIBN) to afford a polymer whose number-average molecular weight is 36 kg/mol; however, the final conversion of the polymer was < 80%. The results of the copolymerization of VCE with styrene (ST) or acrylonitrile (AN) are also discussed.