Substituted 3,4-dihydro-2H-pyrans ($1_{a-e}$) were prepared by (4 + 2) cycloaddition reaction of dimethyl dicyanofumarate with the corresponding electron-rich olefins. The compounds $1_{a-e}$ were ring-open polymerized by cationic initiators to obtain polymers of 1:1 alternating sequence. Polymerizations were carried out with boron trifluoride etherate in methylene chloride at $-78^{circ}C$. All the polymers obtained were soluble in common solvents and were reprecipitated by pouring its chloroform solution into diethyl ether. All the compounds $1_{a-e}$ were not as reactive as the corresponding pyrans derived from ${alpha}$ -cyanoacrylate.