New polymer networks were prepared by free radical initiated copolymerization of crystallizable alpha,omega-bismethacrylate-terminated poly(octadecyl vinyl ether) (polyODVE) with butyl acrylate (BA). The polyODVE bismacromonomers were obtained by end-capping the bifunctionally living cationic polymerization of ODVE with 2-hydroxyethyl methacrylate (HEMA). The segmented networks show a high degree of phase separation over a wide range of compositions. The shape memory properties of a material containing 20 wt.-% of polyODVE are reported.