Glaze flaking is widespread in Hongzhou kiln celadon dating from the Eastern Han to the Tang Dynasty, yet its underlying mechanism cannot be attributed to a single factor. In this study, 11 Hongzhou kiln celadon specimens from the Eastern Han, Southern Dynasties, and Sui–Tang periods were examined using microscopic observation, SEM–EDS, Raman spectroscopy, crack-width measurements, glaze-area analysis, water-absorption tests, and burial environment analysis to investigate the characteristics and causes of glaze flaking. The results show that crazing-crack width is significantly and positively correlated with the extent of glaze flaking. The body–glaze interlayer generally exhibited heterogeneous features, including anorthite crystallization, unmelted quartz grains, bubbles, and locally phase-separated droplets. Anorthite crystals and adjacent regions were frequently associated with crystal-shaped corrosion pits, irregular voids, and localized structural loosening; degraded areas showed depletion of Ca and Si and relative enrichment of Al and Fe. The burial soils were generally neutral to slightly alkaline and showed no evident salt accumulation, suggesting that high salinity was not the primary direct cause of glaze flaking in these samples. These findings suggest that glaze flaking in Hongzhou kiln celadon results from the interaction between firing-induced heterogeneity at the body–glaze interface and prolonged post-burial corrosion. Crazing and interconnected cracks acted as pathways for moisture and soluble ions to penetrate the body–glaze interlayer, triggering selective corrosion of Ca-rich crystalline phases and adjacent glassy phases and ultimately causing interfacial destabilization and glaze loss.