1,6-Anhydro glucose was extracted from a wood tar that is a by-product of charcoal manufacture. After methylation of the 1,6-anhydro glucose, the starting monomer, 1,6-anhydro-2,3,4-tri-O-methyl-beta-D-glueopyranose (LGTME), was obtained. We found that LGTME had high ring-opening polymerizability and polymerized under mild conditions. With BF3OEt2 catalyst under ordinary pressure and N-2 atmosphere at 0 degrees C, LGTME gave high molecular weight of polymer with 1,6-alpha stereoregularity in a high yield, even though benzylated 1,6-anhydro glucose monomer (LGTBE) gave no polymers by the same polymerization conditions. The GPC profile showed two absorptions corresponding to (M) over bar (n) = 272 x 10(3) and (M) over bar (n) = 390 x 10(4) in the proportion of 4.5:1. Furthermore, under high vacuum condition at 0 degrees C, LGTME gave the corresponding polymer and the lower molecular weight increased to (M) over bar (n) = 364 x 10(3). To reveal the high polymerizability of LGTME, two-step polymerization was performed. After the first stage of polymerization under ordinary pressure for 6 h at 0 degrees C, the second LGTME monomer was added to the polymerization mixture and then the polymerization was continued. It was found that the lower molecular weight of the resulting polymer increased to (M) over bar (n) = 394 x 10(3) and the yield was 78%. These results suggest that poly(LGTME) after the first-stage polymerization has stable propagating end which has a restarting ability for the ring-opening polymerization. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1013-1022, 2009