Ions of Li, Na, K, and B were incorporated in Ca-mica, CaMg3Al2Si2O10F2. The crystallization process and the properties of the resulting glass-ceramics were experimentally determined, and the role of the anions and cations is discussed. According to the results, Li, K, and Na ions strongly affected the formation of the crystalline phases. Until 900 °C, pargasite and F-cannilloite amphiboles and KLi-mica were predominately crystallized. The two amphiboles are dissociated, yielding stable forsterite at 900 °C and Ca-mica and spinel at 950 °C. KLi-mica showed remarkable stability and growth within the investigated temperature range, until 1000 °C. The optimum crystallization temperature for the investigated glass-ceramics is between800 °C and 900 °C. The produced glass-ceramics exhibited capability for easy bulk crystallization, high whiteness, translucency, and mechanical and chemical properties suitable for several applications.