The synthesis of three novel graft copolymers consisting of a PVC backbone fitted with polynorbornadiene (PNbd), polyindene (PInd), polycyclohexadiene (PCHD) branches, i.e., PVC-g-PNbd, PVC-g-PInd, and PVC-g-PCHD, is described. The synthesis strategy was to initiate the grafting of norbornadiene (Nbd), indene (Ind), and 1,3-cyclohexadiene (CHD) by a PVC containing similar to 1.6 active (tertary and allylic) chlorines in conjunction with Et2AlCl. The products were characterized by solvent fractionation, molecular weight determination, T-g, and NMR spectroscopy. The effect of temperature on the grafting was investigated in the 20 to -50 degreesC range.