Macrocyclic alpha-(alkoxymethyl)acrylates such as 2-methylene-4-oxa-12-dodecanolide, 2-methylene-4-oxa-16-hexadecanolide, 8,9-benzo-2-methylene-4,7, 10-trioxa-8-dodecen-12-olide and 9, 10-benzo-2-methylene-4,8,11-trioxa-9-tetradecen-14-olide were synthesized and their polymerizability and the stereoregularity of the obtained polymers by radical and anionic methods were investigated. The anionically obtained polymers possessed a normal vinyl polymer structure, and the polymerization with organolithium and Grignard reagents afforded isotactic-rich polymers, whereas the polymers obtained with potassium biphenylide were almost atactic based on their H-1 NMR analysis. The anionically obtained polymers bearing a crown ether-type side chain demonstrated a cobalt ion transport ability as a synthetic ion channel using vesicles prepared with dihexadecyl phosphate.