Reactive polymers possessing both unsaturated double bonds and naphthalene moieties have been designed and synthesized on the basis of the living coordination polymerization of allene derivatives. For the monomers, 1- and 2-allenyloxymethylnaphthalene were prepared from 1- and 2-methylnaphthalene, respectively, and subsequently they were subjected to the coordination polymerization by [(allyl)NiOCOCF3](2) with or without PPh3 ligand. Polymers composed of 1,2- and 2,3-polymerization units were obtained in high yields whose molecular weights and the ratio of 1,2- to 2,3-polymerization could be controlled successfully by the feed ratio of monomer to initiator and the ligand added to the catalyst systems, respectively. From the differential scanning calorimetric analyses, the polymers produced from these monomers were found to possess higher glass-transition temperatures (T-g,) relative to the polymers from benzyloxyallene (i.e., a polymer bearing benzene rings instead of naphthalene moieties). The melting point (T-m,) was observed in the case of the polymer prepared in the absence of Ligands, while that prepared in the presence of PPh3 did not reveal T-m,, indicating that the crystallinity of the polymer is dependent on the ligands used for the polymerization catalysts.