Layered perovskites like titanium-added calcium manganese oxide ceramics have attracted attention as materials that can prevent solar heat absorption by reflecting near-infrared (NIR) radiation better than commercial pigments. However, the mechanism underlying their high NIR reflectivity is unclear. Now, researchers have adopted a combination of experimental and theoretical approaches to provide useful insights into the structure, properties, and functioning of these layered perovskites that can be extended to a broad range of crystalline ceramics.