Appropriate calcium treatments help maintain the appearance, nutritional quality, and postharvest quality of apples, reducing losses during storage. This study investigated the effects of different calcium preparations on the fresh-cut quality and ultrastructure of ‘Starkrimson’ apples. The treatments included control (CK), calcium chloride (T1), sorbitol-chelated calcium (T2), and calcium nitrate (T3). The results demonstrated that sorbitol-chelated calcium significantly inhibited the decline in fresh-cut firmness and pectin content while reducing the increase in cellulose content and minimizing ultrastructural damage. Apples treated with sorbitol-chelated calcium maintained the best fresh-cut hardness and soluble pectin contents, which were 35.71% and 15.42% higher than that of CK on the 12th day, and the cellulose was 27.08% lower than that of CK. Under transmission electron microscopy, the pulp cell surface in the T2 group remained intact, with no bending or deformation, and the middle lamella was well preserved. Additionally, T2 treatment promoted the expression of aroma-related genes during fruit storage. Sorbitol-chelated calcium effectively preserved color and significantly reduced the browning and microbial spoilage of fresh-cut apples, particularly postharvest pathogen growth. The study demonstrates that sorbitol-chelated calcium preserves fresh-cut apple quality by reinforcing cell wall integrity through calcium-mediated crosslinking, suppressing pectin degradation and cellulose accumulation, and activating aroma-related genes (AAT1, AAT2, LOX) to enhance volatile synthesis, thereby reducing microbial spoilage and enzymatic browning during storage.