In the polymerization of racemic L,D-lactide by lithium tert-butoxide as an initiator polyesters with disyndiotactic segments in the polymer chain are obtained. The observation evidences the stereoselectivity leading to an alternating addition of enantiomers to the growing chain during polymerization. The analysis of the carbonyl and methine region in the C-13 NMR spectrum of obtained poly(lactic acid) allowed the calculation of the probability coefficient p(2) determining the amount of disyndiotactic structures in the polymer chain.