The addition of chlorine into a bioactive glass composition is expected to reduce its abrasiveness and increase its bioactivity, which is important for dental applications such as toothpastes. There is a lack of information. and understanding regarding the structural role of Chlorine in chlorine-containing bioactive silicate glasses. This has prompted classical core shell model molecular dynamics simulations of (50 - x/2)CaO-(50 - x/2)SiO2-xCaCl(2) glasses to be performed, where x ranges from x = 0.0 to 43.1 mol % CaCl2. These tertiary glasses ate advantageous for a fundamental study because they do not have additional network formers (e.g., phosphorus pentoxide) or modifiers (e.g., sodium) typically found in bioactive glass compositions. The (50 - x/2)CaO-(50 - x/2)SiO2-xCaCl(2) glasses were seen to become phase-separated around the x = 16.1 mol % CaCl2 composition, and chlorine predominantly coordinated with calcium. These findings provide a solid foundation for further computational modeling, work on more complex chlorine - containing bioactive glass compositions.