The crystal structure of CaZr(PO4)2 has been revised by ab initio Rietveld analysis of X-ray powder diffraction data. At room temperature, CaZr(PO4)2 crystallizes in the orthorhombic space group Pna21 (Z = 4). Differential thermal analysis suggests a reversible second order transition at 1000 °C confirmed by high temperature XRD analysis that brings out the existence of a high temperature form, very similar to the room temperature one, but more symmetrical (Pnma, Z = 4). Analysis of the crystal parameters evolution during heating reveals that CaZr(PO4)2 exhibits a quite low thermal expansion coefficient of 6.11·10−6 K−1. This value stems from a combination of several mechanisms, including Coulombic repulsion and bridging oxygen rocking motion.