Abstract: High-temperature Raman spectroscopy and optical microscopic observations have revealed a new metastable polymorph of CaAl₂Si₂O₈ composition, which brings to four the number of known crystalline phases in this system. Similar to the metastable monoclinic pseudo-orthorhombic and pseudo-hexagonal phases, the new polymorph nucleates prior to anorthite, at around 1545 K, and its pseudo-liquidus temperature is 1700 ± 10 K. It can also be formed from the transformation of the pseudo-hexagonal phase at 1050 K. The actual structure of this new crystalline form is unknown, but its Raman spectrum indicates that it is most likely a 6-membered alumino-silicate framework. We have obtained all three metastable phases as pure single crystals using wire loop heating techniques, and have studied their structures via Raman spectroscopy up to their metastable melting points or transformation temperatures.