The alternating copolymerizations of carbon monoxide with the electron-poor bicyclic olefins, diethyl bicyclo[2.2.1]hepta-2,5-diene-2,3-dicarboxylate (1) and diethyl 7-oxabicyclo[2.2.1]hepta-2,5-diene-2,3-dicarboxylate (2), is achieved with neutral palladium(II) initiators. These Pd(II) complexes utilize a sigma,pi-alkyl ligand, a halide anion, and 1 equiv of a stabilizing donor ligand (pyridine or triphenylphosphine). The preferred catalyst, due to reactivity and stability, is iodo(endo-6-phenyl-2-norbornene-endo-5 sigma,2 pi)(triphenylphosphine)palladium(II) (6). This initiator produces living copolymerizations of 1 with CO in the presence of H2O and O-2. The polymer isolated, poly(1-alt-CO), retains the Pd as the endgroup, and can be used to reinitiate copolymerization leading to chain extension or diblock copolymer formation. Both of the copolymers poly(1-alt-CO) and poly-(2-alt-CO) undergo retro Diels-Alder reaction to produce furan derivative 7 and a new cross-conjugated material, poly(ketovinylene:) (PKV). While the temperature for complete conversion of poly(1-alt-CO) is ca. 280 degrees C, poly(2-alt-CO) goes to completion at room temperature and above. During this thermal conversion, the polymer undergoes melt flow that is assisted by the ejected furan solvent, allowing for the fabrication of wires and free-standing films of the conjugated material.