Star-shaped polymers bearing three, four, and six poly(L-lactide) (PLA) arms have been prepared starting from trimethylolpropane (3 OH), di(trimethylolpropane) (4 OH), and dipentaerithritol (6 OH) and L,L-dilactide (LA) monomers. Initiator/catalyst tin octoate was used (bulk polymerization, 120 °C). In liquid chromatography at the critical point of adsorption, the elution volumes of the resulting star-shaped PLAs depend exclusively on the number of arms. Thus, in the first dimension of two-dimensional liquid chromatography, it is possible to observe separately various star-shaped polymers. In the second dimension, size exclusion chromatography provides information on the molar masses. Agreement between the assumed and the resulting PLA structures has been confirmed this way.