The physical aging behavior of amorphous polylactide constrained against polystyrene in layers of 300 nm, thanks to the layer–multiplying co–extrusion process, was investigated by fast–scanning calorimetry (FSC). By cooling down the sample from the liquid state to the glassy one at very fast scanning rates, it was possible to investigate the structural relaxation of the polymer glass at high temperatures for which the time needed to reach the equilibrium was shortened. Therefore it was possible to perform the study of physical aging in experimental conditions providing an expanded view of the structural relaxation for short aging times. Taking benefit of this property, it was highlighted that the aging kinetics of polylactide occurred significantly slower in the multilayer film, in comparison with a bulk amorphous film. The process of recovery in the multilayer system was found to occur at similar rates, or even slower, than in a three–layer film in which polylactide reached its maximum extent of crystallinity. This was attributed to mobility hindrance that might be inherent to the extrusion conditions or associated with the presence of capped interfaces with polystyrene.