2-Methoxy-6-methyl-3,4-dihydro-2H-pyran ($1_a$), 2-ethoxy-3,6-dimethyl-3,4-dihydro-2H-pyran ($1_b$), and 2-ethoxy-3-methyl-6-ethyl-3,4-dihydro-2H-pyran ($1_c$) were prepared by (4 + 2) cycloaddition reaction from the corresponding vinyl ketones and alkyl vinyl ethers. Compounds $1_{a-c}$ were ring-open polymerized by cationic catalyst to obtain alternating head-to-head (H-H) copolymers. For comparison, copolymer of head-to-tail (H-T) was also prepared by free radical copolymerization of the mixture of the corresponding monomers. The H-H copolymer exhibited some differences in its $^1H$ NMR and IR spectra. However, significant differences were showed between the H-H and H-T copolymers in the $^{13}C$ NMR spectra. Also noteworthy was that$T_g$ value of H-H copolymer was higher than that of the corresponding H-T structure. Decomposition temperature of the H-H copolymer was lower than that of the H-T copolymer. All the H-H and H-T copolymers were soluble in common solvents.