Two types of microcontainers were prepared by using the adsorption of polyamide on the surface of micrometer-sized inorganic porous calcium carbonate microparticles followed by thermal conversion of the polyamide layers into polyimide coatings. The effect of the preparation conditions on the structure and morphology of the microcontainers was studied by transmission electron microscopy and scanning electron microscopy. The smoothest and defect-free coatings were prepared using polyethylenimine as the supporting polymer. The thickness of the polyamide/polyimide shells was estimated by atomic force microscopy and scanning electron microscopy between 50 and 150 nm depending on the quantity of the layers. The water-soluble antibiotic, doxorubicin hydrochloride, was used as a model compound to demonstrate the efficiency of the microcontainers for encapsulation. The resistance of the novel microcontainers to solvent treatment was visualized by the confocal scanning fluorescence microscopy. It was demonstrated that the combination of the high thermal and chemical resistance of polyamide/polyimide shell and the sorption capacity of the CaCO3 is very useful for development of highly protective microcontainers and thermal detectors for smart fabrics.