This review focuses on recent advances in the synthesis and characterization of calcium aluminate glasses and the effects of various ion additions/substitutions on the processing and properties of these glasses. Calcium aluminate-based glasses are of great scientific and technological interest because of their extraordinary combination of broad spectral transparency, refractory nature, high mechanical stiffness and hardness, superior chemical durability, and low cost compared to glasses formed in many other families. Current obstacles for large-scale manufacturing include high melting temperature and tendency for devitrification, which have so far received relatively little attention in the literature. The problem with devitrification can be partially mitigated through addition of certain oxides (MgO, GeO 2, BaO, etc.) without severely impairing the optical transmission for applications as low-loss optical materials. Suggestions for future research are also discussed, including improved understanding of composition-structure-property relationships, possible improvements of CaO-Al 2O 3 glass fiber fabrication, computational modeling to enable an improved glass-forming ability, and detailed analysis of thermophysical properties for achieving the optimal composition without compromising performance.