The stereochemical configuration of poly(glycidyl methacrylate) has been analyzed by H-1 and C-13 NMR spectroscopy. Homopolymers prepared by free radical polymerization in solution and in bulk at 80 degreesC are predominantly syndiotactic and follow the Bernoullian distribution of tactic sequences with isotactic parameters, sigma (s) = 0.24 and sigma (b)= 0.27, very close to that of the free radical polymerization in solution of methyl methacrylate, sigma (s) = 0.23. This information is of primary importance for polymer characterization, but it also provides knowledge about the reaction mechanism. (C) 2001 Published by Elsevier Science Ltd.