AbstractSoluble polymer with methylene‐1,4‐dioxane‐2,3‐diymethylene (75 − 65 mole‐%) and 2‐[(vinyloxy)ethoxy]ethylene structural units (25 − 35 mole‐%) were obtained in the radical polymerization of ethylene glycol divinly ether (EGVE) in benzene at conversions of about 30 – 45%. It was found that in the radical polymerization of EGVE the rate of polymerization is proportional to the 1,5th power of monomer concentration and to the 0, 6th power of initiator concentration. On the other hand, a soluble polymer with 1,4‐dioxepane‐5,7‐diylmethylene units was obtained from cationic polymerization of EGVE in dichloromethane by using iodine as as catalyst. Moreover, the photocrosslinking reactions by irradiation with UV light of the radically obtained polymer having pendant vinyloxy groups with dithiols or by diazonium tetrafluro