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Fired clay ceramics are promising materials for TES, thanks to their thermal stability, availability worldwide, low cost and easy shaping and handling. However, their thermo-physical and thermo-mechanical properties have to be improved. For the first time, clay-phosphate ceramics, with synthetic calcium hydroxyapatite (TCP, Ca10(PO4)6(OH)2) as additive, were developed in view of TES application. A parametric study was carried out for different clay/TCP mixtures, wherein the TCP percentage varies from 0 to 16.7 wt%. The best material containing 4.7 wt% TCP allowed increasing up to 20% of the thermal conductivity and 23% of the mechanical strength. Moreover, it was thermally stable up to 1000 °C. These original results demonstrate the suitability of these new materials for heat storage in energy systems such as in a concentrated solar power (CSP) plant, or in a unit of heat recovery from an industrial waste heat source.