The invention discloses preparation and application of PEG/Dex dual-aqueous-phase based calcium carbonate/calcium alginate composite microcapsules. The composite microcapsules are produced by taking dual-aqueous-phase (glucan/polyethylene glycol) liquid droplets as a template. The composite microcapsules are good in monodispersity, and the particle size can be accurately regulated and controlled from several microns to several millimeters. The microcapsules are of hollow structures, capsule walls are of double layers, the thickness of the capsule walls is controllable (about 1/50 to 1/4 the particle size of the microcapsules), inner sides of the capsules are of dense calcium carbonate layers, and outer sides of the capsules are of calcium alginate layers. Compared with pure calcium alginate microcapsules, the microcapsules have good mechanical strength and a dense capsule wall structure, the damage to capsule layers caused by a shearing force is avoided, and the leakage of contents isinhibited. The microcapsules can be used for constructing a low-leakage drug transport system and can also be used for preparing an immobilized enzyme carrier, which is high in number of times of recycle, long in preservation time and difficult in swelling. According to the preparation and the application, the application of calcium alginate microcapsules in the fields of biomedicines, food industry, chemical industry for daily use, enzyme engineering and the like is extended.