The diffusional Deborah number, De, defined as the ratio of characteristic relaxation time to characteristic diffusion time was determined as a function of concentration and temperature in the dodecane transport process in polystyrene. The characteristic relaxation time was obtained from the viscoelastic properties of dodecane/polystyrene systems measured by a dynamic mechanical analyzer. The characteristic diffusion time was obtained from the concen-tration and temperature dependence of the diffusion coefficient measured by NMR PGSE method. Above the room temperature the Deborah number changed significantly during isothermal transport process; however, the transport mechanism did not deviate from the Fickian transport as the order of De was still greater than 1. Around the room temperature the transport mechanisms represented by the resulting diffusional Deborah number changed significantly as the order of magnitude approached 1 with the temperature decreasing from 50℃ to the room temperature. The transport mechanism predicted from the diffusional Deborah number was verified by the diffusional exponent, n, of an exponential time-dependence of the penetrant uptake.