alpha-(Alkoxymethyl) acrylates, such as methyl alpha-(phenoxymethyl) acrylate, benzyl alpha-(methoxymethyl) acrylate (BMMA), benzyl alpha-(benzyloxymethyl) acrylate, and benzyl alpha-(tert-butoxymethyl) acrylate, were synthesized, and their polymerizability and the stereoregularity of the polymers obtained by radical and anionic methods were investigated. The radically obtained polymers were found to be atactic by C-13- and H-1- NMR analyses, but the polymers obtained with lithium reagents in toluene at -78 degrees C were highly isotactic. Further, it is noteworthy that isotactic polymers were also produced with lithium reagents even in tetrahydrofuran. Effects of polymerization temperature and counter cation on stereoregularity were clearly observed in the polymerization of BMMA, and a potassium reagent afforded an almost atactic polymer.