Developing　high-performance　Ca-based　materials　that　can　work　for　long-term　heat　transfer　and　storage　in　concentrated　solar　power　plants　is　crucial　to　achieve　the　large-scale　conversion　of　solar　photon　fluxes　to　dispatchable　electricity.　This　work　demonstrates　that　a　series　of　Mn,　Zr　co-doped　CaCO3　nanomaterials　with　the　3D　ordered　macroporous　(3DOM)　skeletons　are　successfully　prepared　by　a　novel　strategy　of　templated　metal　salt　co-precipitation.　The　characterization　results　indicate　that　a　majority　of　Zr　and　Mn　are　atomically　dispersed　into　the　highly-crystallized　CaCO3　framework,　whereas　a　minor　amount　of　Mn　is　present　in　the　form　of　CaMnO3　nanoparticles　(NPs).　The　optimal　3DOM　material　made　by　templating　with　PS　microspheres　with　a　diameter　of　≈350 nm,　3DOM-Ca80Mn10Zr10,　shows　a　solar　light　absorptance　of　≈74.1%　and　an　initial　energy　storage　density　of　1706.4　kJ kg−1.　Importantly,　it　gives　an　impressive　energy　storage　density　loss　of　＜ 6.0%　and　maintains　above　1600 kJ　kg−1　after　125　cycles.　The　density　functional　theory　calculations　reveal　that　the　co-doping　of　Mn　and　Zr　into　the　CaO　crystal　lattice　offers　a　strong　affinity　to　[Ca4O4]　clusters,　as　a　result,　the　anti-sintering　of　CaO　NPs　is　significantly　enhanced　under　high　temperature.　©　2024　The　Author(s).　Advanced　Science　published　by　Wiley-VCH　GmbH.