The gel properties of sodium alginate (SA) have been revealed to be strongly correlated with its ratio of D-mannuronate to L-guluronate (M/G ratio). Herein, we focused on SA with different M/G ratios to conduct an in-depth study on the effect of the M/G ratio difference on physicochemical stability and calcium release behavior of the Pickering emulsion stabilized by calcium carbonate (CaCO3). The oil phase was added to the aqueous phase, prepared by SA with different M/G ratios (2.23, 0.89, and 0.56) and CaCO3, for one-step shearing to obtain the E1, E2, and E3 emulsions, respectively. The results of the particle size, microstructure, long-term stability, rheological, and microrheological properties of the emulsions showed that the E3 emulsion, prepared by SA with a smaller M/G ratio, had a smaller particle size and has remained in a flow condition during the long-term storage, while the E1 and E2 emulsions had a gelation behavior and a stronger viscoelasticity. Moreover, the emulsion, as a liquid calcium supplement, is not only convenient for oral intake while meeting the calcium needs of the body, but also controls the release of Ca2+. The calcium release of the emulsions in a simulated gastric environment demonstrated that the calcium release ratio increased with the decrease of SA concentration, with the increase of M/G ratio, and with the decrease of oil phase volume.