Abstract: Synchrotron radiation, high-resolution transmission electron microscopy (HRTEM), X-ray powder diffraction, and Raman spectroscopy were used to study the structure and thermal behavior of malayaite, CaSnSiO5. No indications of deviation from A2/a symmetry and no structural transitions were observed between 100 and 870 K. HRTEM revealed that the material is free of domains and antiphase boundaries. However, the lattice constants, cell volume, and Raman-active phonons show a thermal discontinuity near 500 K, which is possibly related to variation of the coordination sphere around the highly anisotropic Ca position.