Allyl ethers are readily polymerized using a new polymerization reaction termed : transition metal-catalyzed tandem isomerization and cationic polymerization. Empoloying dicobalt octacarbonyl in combination with organosilanes, polymerization takes place rapidly and exothermically to give high molecular weight polymers. In this first article, the concepts leading to the discovery of this novel type of polymerization are presented along with the results of initial studies.