An investigation of the diffusional mobility of a bioactive compound (caffeine) within the high-solid (80.0% w/w) matrices of glucose syrup and ?-carrageenan plus glucose syrup exhibiting distinct mechanical glass transition properties is reported. The experimental temperature range was from 20 to -60 °C, and the techniques of modulated differential scanning calorimetry, small deformation dynamic oscillation in shear, and UV spectrometry were employed. Calorimetric and mechanical measurements were complementary in recording the relaxation dynamics of high-solid matrices upon controlled heating.