The present study utilizes vibrational sum frequency generation (SFG) spectroscopy to study changes in the surface crystallinity of various peracetylated sugars, a class of materials that have a high affinity for carbon dioxide (CO2). Studies of the solid-air interface of acetylated, beta-cyclodextrin (Ac-beta-CD) and sucrose octaacetate (SOA) show that diffuse reflectance SFG spectroscopy is sensitive to changes in crystallinity from processing with either heat or solvation in CO2, due to the loss of signal after glassification occurs. beta-D-Glucose pentaacetate (Ac-beta-GLC) was used as a control for this experiment due to the fact that it does not undergo a crystalline phase transition, regardless of processing conditions. The crystalline to amorpohous transitions of these bulk materials were verified using differential scanning calorimetry (DSC) as a function of thermal and CO2 processing. In addition, preliminary results suggest that the SFG technique is sensitive in detecting the degree of crystallinity at the interface as a result of incomplete processing and presents new opportunities for the examination and detection of surface crystallinity changes.