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In order to better manage the peeling degree and avoid unnecessary losses, the current work aimed to explore the peeling mechanism of a novel peeling technology, high-humidity hot air impingement blanching (HHAIB). The relationships between HHAIB peeling performance and the changes in skin temperature, skin structure, water state, pectin fractions content, and skin mechanical properties of tomatoes were analyzed. Results showed, after HHAIB treatment, the epicuticular wax was disrupted, the skin exhibited more and longer random cracks, the degradation of inner skin tissue was observed by transmission electron microscopy, the free water percentage increased resulting in water loss in the whole tomato, the water-soluble pectin contents decreased in tomato fleshes, while the contents of chelate-soluble pectin and sodium-carbonate-soluble pectin increased. HHAIB heating reduced the elongation at break, and increased Young's Modulus of tomato peel. This study revealed the HHAIB peeling mechanism and provided new insights for developing HHAIB peeling technology.