Calcium-chelated polysaccharides have been increasingly considered as promising calcium supplements. In this study, degraded fucoidans (DFs) with different molecular weights (Mws) were prepared after UV/H2O2 treatment; their calcium-chelating capacities and intestinal absorption properties were also investigated. The results showed that the calcium-chelating capacities of DFs were improved with a decrease in Mw. This was mainly ascribed to the increased carboxyl content, which was caused by free-radical-mediated degradation. Meanwhile, the conformation of DF changed from a rod-like chain to a shorter and softer chain. The thermodynamic analysis demonstrated that DF binding to calcium was spontaneously driven by electrostatic interactions. Additionally, DF-Ca chelates with lower Mw showed favorable transport properties across a Caco-2 cell monolayer and could effectively accelerate the calcium influx through intestinal enterocytes. Furthermore, these chelates also exhibited a protective effect on the epithelial barrier by alleviating damage to tight junction proteins. These findings provide an effective free-radical-related approach for the development of polysaccharide-based calcium supplements with improved intestinal calcium transport ability.