AbstractA exploratory study on the copolymerizability of 2‐vinyl‐1,3‐dioxane (VD) has been carried out.VD was polymerized with styrene, vinyl acetate, methyl methacrylate, and acrylonitrile. Acrylonitrile was the only one which provided copolymerization products. For the acrylonitrile (M1)‐VD (M2) pair,r1= 3.64 ± 0.1 andr2= 0.057 ± 0.01 at 70°C. The transfer reactions of a series of 1, 3‐dioxane compounds in the styrene polymerization were investigated, with the result that the acetalic hydrogen is responsible for the transfer values found. VD was also copolymerized with maleic anhydride yielding alternatin