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Novel phase change microcapsules (micro-PCMs) composed of a paraffin core and aCe³⁺-doped calcium carbonate (CaCO₃:Ce³⁺) shell was designed by self-assembly precipitation. The morphology, composition, and structure of microcapsules were analyzed by scanning electron microscopy, X-ray diffraction, energy-dispersive spectrometry, and X-ray photoelectron spectroscopy. The paraffin@CaCO₃:Ce³⁺ microcapsules had regular spherical shapes and core–shell structures. Rare earth element Ce³⁺ was successfully introduced into the crystal lattice of CaCO₃, partially replacing calcium ions. The microcapsules had good thermal regulation ability, high sealing, and energy storage efficiency. Most importantly, the luminescence intensity of paraffin@CaCO₃:Ce³⁺ microcapsules were further enhanced with the increase of Ce³⁺ concentration. The paraffin@CaCO₃:Ce³⁺ microcapsules developed in this study …