Free-radical-initiated grafting of maleic anhydride (MA) onto a polylactide (PLA) backbone was performed by reactive extrusion. A concentration of 2 wt % MA in the presence of 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane (Lupersol 101) as the free-radical initiator was used for all experiments. Two reaction temperatures were studied (180 and 200 degrees C) with a peroxide initiator concentration between 0.0 and 0.5 wt %. Under these conditions, between 0.066 and 0.672 wt % MA was grafted onto the PLA chains. Triple-detector size-exclusion chromatography (TriSEC), melt flow index (MFI), and thermal gravimetric analysis (TGA) were used to characterize the maleated PLA polymers. Increasing the initiator concentration resulted in an increase in the grafting of MA, as well as a decrease in the molecular weight of the polymer. The maleation of PLA proved to be very efficient in promoting strong interfacial adhesion with corn native starch in composites as obtained by melt blending.