Abstract :  The epimerization of polylactide is reported in the presence of 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) at 105 °C in toluene. The extent of the reaction depends on the amount of TBD introduced and the reaction time. Up to ca. 46% D units can be formed starting from poly(l-lactide) in the presence of 5 mol% TBD. The epimerization rate is slightly higher for D-stereoisomers vs. L-stereoisomers. From the decrease of the number-average molecular weight observed, a concomitant chain scission reaction is observed. A possible mechanism based on a nucleophilic attack of TBD is proposed based on NMR analyses, notably DOSY, MALDI ToF mass spectrometry and IR spectroscopy. The implications of the work in the field of polymer synthesis and chemical recycling of polylactide are discussed.