In this study, the role of water and the impact of the glass to rubber transition on aroma mass transport through hydroxypropyl maize starch films were followed. The permeability of four aroma compounds (ethanol, pyrazine, menthone, and decanone) was monitored by atmospheric pressure chemical ionization mass spectroscopy. The increase in water content within the film promoted greater water diffusion and film flexibility and resulted in enhanced transport of the four aroma compounds through the film. At low water contents in the glassy state, the permeability of ethanol was much higher than those of the other three compounds, which was attributed to its low molecular volume and greater solubility in starch. The structural changes induced by the glass transition resulted in the hydroxypropyl maize starch films displaying poor barrier behavior in the rubbery state for all the aromas studied.