The composition of lactide stereoisomeric mixtures was quantified by GC-Polarimetry. Compared with GC-HPLC, it is suitable to all of lactide samples and more time-saving. The D-lactide content is a function of specific rotation and meso-lactide content. A small amount of impurities in samples little interferes the quantitative analysis. The L-lactide specific rotation is −266.3° (dichloromethane) and −298.8° (toluene).