The effect of stereocomplexation on the stability and migration resistance of polylactide during microwave and conventional heating in contact with different food simulants was evaluated. The heating effects were followed through mass loss measurements, molecular weight measurements and identification of the individual migrants by electrospray ionization-mass spectrometry (ESI-MS). Increased mass losses were observed as a function of time and temperature, but approximately 50% smaller mass losses were always measured for PLA stereocomplex as compared to the corresponding regular PLLA material. The stability of the stereocomplex material was, thus, significantly higher. Microwave heating increased the mass loss as compared to the conventional heating at the same time and temperature. This effect was especially significant when 10% ethanol was used as food simulant instead of water. The amount of water-soluble migrants was in most cases under the detection limits, but when heating temperature was increased to 95°C, ESI-MS revealed the formation of homologous series of linear lactic acid oligomers. Results indicate that PLA stereocomplex materials could have potential in single-use microwave applications.