Unsaturated poly(ethylene-co-5-vinyl-2-norbornene) was synthetized using the [Ph2C(Flu)(Cp)]ZrCl2 metallocene/methylaluminoxane (MAO) catalyst system. H-1 and C-13 NMR spectra of the copolymer were assigned by means of DEFT, homonuclear 2D H-1-H-1 COSY, and heteronuclear 2D H-1-C-13 correlation NMR experiments. The used catalyst system produces mainly isolated 5-vinyl-2-norbornene (VNB) sequences. VNB is incorporated selectively via the cyclic double bond. The unreacted double bond of the copolymer exists in the 5-endo:5-exo positions (3:1). Both isomers of VNB are polymerized with the same propability.