Telechelic dihydroxy poly(2-vinylpyridine) (THPVP) samples with different molecular weights were synthesized by using lithium a-methylnaphthalene as an anionic initiator in mixed solvents of benzene and tetrahydrofuran (THF). Then multiblock copolymers of poly(2-vinylpyridine) (P2VP) and polyoxyethylene (PEO) were obtained by condensing THPVP and PEO with dichloromethane in the presence of potassium hydroxide. The effects of reaction time, molecular weight of PEO and THPVP, and raw meal ratio PEO/THPVP (w/w) were investigated. The best conditions were found. The copolymers can be purified by water and toluene. The purified copolymers were characterized by infrared (IR) and H-1 nuclear magnetic resonance (H-1-NMR). The PEO segment content was calculated from the integral curve of H-1-NMR spectra. The results showed that these multiblock copolymers were connected through oxymethylene. (C) 2003 Wiley Periodicals, Inc.