A new class of polymer electrolytes, based on the interpenetrating polymer network approach, was obtained starting from functionalised macromers, of poly-ether nature, in the presence of a lithium salt (LIBF4, LiClO4, LiCF3SO3) and propylene carbonate (PC) or tetraethyleneglycol dimethylether (TGME), as plasticizers. The macromers were synthesised by living polymerisation employing a HI/I-2 system as the initiator. The macromer has a polymerisable end group, which can undergo radical polymerisation, attached to a monodisperse poly-vinylether, containing suitable ethylene oxide groups for ion coordination. Monomers and macromers were characterised by FTi.r., u.v.-vis, H-1- and C-13-n.m.r. Self-consistent and easily handled membranes were obtained as thin films by a dry procedure using u.v. radiation to polymerise and crosslink the network precursors, directly on suitable substrates, in the presence of the plasticizer and the lithium salt. The electrolytic membranes were studied by complex impedance and their thermal properties determined by differential scanning calorimetry analysis. Ionic conductivities (sigma) were measured for PC and TGME-based membranes at various plasticizer and salt contents as a function of T (60 to -20 degrees C). LiClO4/PC/PE electrolytes, with 3.8% (w/w) salt and 63% PC, have the highest a (1.15 x 10(-3) and 3.54 x 10(-4) S cm(-1) at 20 degrees C and -20 degrees C, respectively). One order of magnitude lower conductivities are achieved with TGME; samples with 6% (w/w) LiClO4 and 45% (w/w) TGME exhibit sigma values of 2.7 X 10(-4) and 2.45 X 10(-5) S cm(-1) at 20 degrees C and -20 degrees C.