To reduce grievous ecological environment pollution and protein resource waste during mung bean starch production, mung bean peptides-calcium chelate (MBP-Ca) was synthesized as a novel and efficient calcium supplement. Under the optimal conditions (pH = 6, temperature = 45 °C, mass ratio of mung bean peptides (MBP)/CaCl2 = 4:1, MBP concentration = 20 mg/mL, time = 60 min), the obtained MBP-Ca achieved a calcium chelating rate of 86.26%. MBP-Ca, different from MBP, was a new compound rich in glutamic acid (32.74%) and aspartic acid (15.10%). Calcium ions could bind to MBP mainly through carboxyl oxygen, carbonyl oxygen, and amino nitrogen atoms to form MBP-Ca. Calcium ions-induced intra- and intermolecular interactions caused the folding and aggregation of MBP. After the chelation reaction between calcium ions and MBP, the percentage of β-sheet in the secondary structure of MBP increased by 1.90%, the size of the peptides increased by 124.42 nm, and the dense and smooth surface structure of MBP was transformed into fragmented and coarse blocks. Under different temperatures, pH, and gastrointestinal simulated digestion conditions, MBP-Ca exhibited an increased calcium release rate compared with the conventional calcium supplement CaCl2. Overall, MBP-Ca showed promise as an alternative dietary calcium supplement with good calcium absorption and bioavailability.