The effect of surface modification on the degradation process and degradation product patterns of degradable polymers is still a basically unexplored area even though a significant effect can be expected. Polylactide (PLA) and PLA grafted with acrylic acid (PLA-AA) were, thus, subjected to hydrolytic degradation, and water-soluble degradation products were determined by electrospray ionization-mass spectrometry (ESI-MS) after different time periods. Low molar mass compounds migrated from surface-grafted PLA already during the first 7 days at 37 degrees C, while it took 133 days in the case of nongrafted PLA before any low molar mass compounds were detected in the aging water. In addition, the degradation product pattern of surface-grafted PLA showed significant variation as a function of hydrolysis time with the evolution of short and long AA-grafted lactic acid oligomers as well as plain lactic acid oligomers after different time periods. The degradation product pattern of plain PLA consisted of lactic acid and its oligomers with up to 13 lactic acid units. Surface grafting, thus, changed the degradation product patterns and accelerated the formation of water-soluble degradation products.