Calcium Tschermak’s pyroxene (CaTs), CaAlAlSiO6, is well known as an important component in pyroxene. It is a member of the Ca clinopyroxene group in which Al dominates in the M1 site. Pyroxenes with more than 80 mol% CaTs were observed previously in Ca-,Al-rich refractory inclusions (CAI) from five carbonaceous chondrites. This study re-investigated the near end-member CaTs in the Allende and Murray chondrites. Electron backscatter diffraction (EBSD) is used to establish that its crystal structure is monoclinic, C2/c; a = 9.609 Å, b = 8.652 Å, c = 5.274 Å, β =106.06°, V = 421.35 Å3, and Z = 4. Its EBSD pattern is an excellent match to that of synthetic CaAlAlSiO6 with the C2/c structure. MicroRaman is also carried out to confirm the crystal structure. The Allende CaTs, with 46.00 wt% Al2O3 and 97 mol% Al in the M1 site, has the formula Ca1.02(Al0.97Fe0.01Mg0.01)∑0.99(Si1.00Al1.00)∑2.00O6. It occurs as micrometer-sized crystals along with melilite, hibonite, perovskite, spinel, corundum, Ti3+-rich pyroxene, and grossular in a fluffy Type A CAI. It is probably a secondary phase resulting from the alteration of gehlenitic melilite. The CaTs in Murray, with a formula Ca0.98(Al0.81Mg0.16Ti0.044+)∑1.01(Si1.11Al0.89)∑2.00O6, occurs with hibonite and Al-rich diopside in a glass-free refractory spherule. This sample formed by solidification of a once-molten droplet early in the history of the solar system.