Dielectric spectroscopy has unique advantages in monitoring drug release. In this work, a dielectric measurement was carried out on the release of the substances of microcapsule-immobilized composite capsules, which were fabricated by encapsulating the Perinereis aibuhitensis extract-loaded gum Arabic/gelatin microcapsules (PaE: GA/GE-MCs) in calcium alginate hydrogel (PaE: CA/GA/GE-CCs). We established the dielectric model of PaE: CA/GA/GE-CCs and got in-depth information on the systems. There are two relaxations in the dielectric spectroscopy, both of which are caused by interfacial polarization. The relaxation mechanisms correspond to the interfacial polarization of the PaE-loading core/calcium alginate shell interface and the calcium alginate shell/solution interface, respectively. Besides, the swelling of composite capsules and substance migration in the composite capsules were observed by analyzing phase parameters. Finally, the characteristic release of calcium alginate composite capsules was confirmed, and the substance release mechanism of composite capsules, namely, the swelling-diffusion mechanism, was obtained.