New types of composites were obtained by an autotemplate method for assembling hollow CaCO capsules by using pH-sensitive polymers. Five pectin samples, which differ in the methylation degree and/or amide content, and some nonstoichiometric polyelectrolyte complex dispersions, prepared with the pectin samples and poly(allylamine hydrochloride), were used to control the crystal growth. The morphology of the composites was investigated by scanning electron microscopy, and the polymorphs characteristics were investigated by FTIR spectroscopy. The presence of the polymer in the composite particles was evidenced by X-ray photoelectron spectroscopy, particle charge density, and zeta-potential. The new CaCO/pectin hollow capsules were tested as a possible matrix for a tetracycline hydrochloride carrier. The kinetics of the drug release mechanism was followed using Higuchi and Korsmeyer-Peppas mathematical models.