X-ray computed tomography technique was used to observe microstructure formation during freeze-drying. A specially designed vacuum freeze-drying stage was equipped at the X-ray CT stage, and the frozen and dried microstructures of dextrin solutions were successfully observed. It was confirmed that the many parts of the pore microstructures formed as a replica of the original ice microstructures, whereas some parts formed as a consequence of the dehydration dependent on the relaxation level of the glassy phases, suggesting that the post-freezing annealing is advantageous for avoiding quality loss that relates to the structural deformation of glassy matters. Keywords: freeze-drying; X-ray CT; ice microstructure; glassy state