Conformational characteristics of poly(lactide)s have been investigated by density functional theory and ab initio molecular orbital (MO) calculations and NMR experiments on model compounds. Characteristic ratios, configurational entropies, and internal energies of poly(L-lactide) and poly(DL-lactide), whose stereosequences were generated by Bernoulli and Markov stochastic processes, were calculated under the refined rotational isomeric state scheme with conformational energies and geometrical parameters derived from the MO calculations. In terms of the conformational characteristics thus revealed, we have elucidated the reason why unperturbed chain dimensions determined experimentally for poly(L-lactide) are scattered considerably and, furthermore, discussed crystallization and crystal structures of poly(L-lactide) and molecular characteristics of poly(DL-lactide) synthesized from rac-lactide with stereospecific polymerization catalysts. (C) 2014 Elsevier Ltd. All rights reserved.