This paper describes the synthesis of polyurethane networks based on partly hydroxymodified poly(chloroethyl vinyl ether)s and examines the possibility to introduce various amounts of hydroxy groups in the network. Poly(chloroethyl vinyl ether)s are prepared by living-type cationic polymerization initiated by the HI/ZnCl2 system. Introduction of hydroxyl groups along the chain, in controlled amount, is then achieved in a two-step process involving the reaction of a fraction of the pendant chloride groups with a carboxylic salt, followed by alkaline hydrolysis. Finally the corresponding polyurethane networks- with or without remaining hydroxy functions- are obtained by reaction with hexamethylene diisocyanate in different proportions. Preliminary study of the mechanical properties of the networks are also reported.