The synthesis of novel polyoctenamers with pendent functionalized cyclotriphosphazenes as amphiphilic lithium ion conductive membranes is described. Cyclotriphosphazene monomers were functionalized with one cycloocteneoxy substituent per ring. Two different types of monomer units, one with oligoethyleneoxy cation coordination side groups and the other with hydrophobic fluoroalkoxy side groups, were then prepared. The syntheses of these monomers, their ring-opening metathesis copolymerization, and the characteristics of the resultant polymers are discussed, with an emphasis on the dependence of ionic conductivity and hydrophobicity on polymer composition.