The use of butyllithium and butylmagnesium in the polymerization of racemic lactide leads to the formation of polylactide with a partially disyndiotactic structure, A coefficient of stereoselectivity p(2) which describes the content of disyndiotactic structures appears to be higher for the lithium initiator; however an increase in the concentration of this initiator tends to enhance an intermolecular transesterification process thus leading to the formation of totally random structures in a polylactide chain. In contrast, in the case of butylmagnesium, an increase in the initiator concentration does not induce the intermolecular transesterification processes.