Dextrin solutions with organic volatiles (straight-chain fatty alcohols: C1-C10 and straight-chain ethyl esters: C2-C10) were freeze-dried under the conditions of controlled heating and vapor transfer. During drying, the products were heated by radiative heating. Vapor transfer from the dryer was controlled by adjusting the orifice between the drying chamber and condenser. Collapse and/or microcollapse formation in the freeze-dried products was dependent on the combination of the employed drying conditions. The degree of collapse was evaluated by analyzing X-ray-computed tomography images. We observed that the degree of collapse is correlated to the characteristics of the freeze-dried products, such as their crystallinity, dissolution ability, and retention of organic volatiles. Retention, in turn, was dependent on the type of volatiles and was significantly affected by the processing conditions. A high loss of volatiles was observed under the freeze-drying conditions that led to a high degree of collapse. Furthermore, we demonstrated that the degree of collapse in dextrin matrices could be evaluated by a simple compression test on the powders obtained by grinding the freeze-dried products.