A family of new glass-ceramic materials, of the general formula (25-x)CaO.xBaO.yMgO. zAl(2)O(3).5OSiO(2), where x=1, 2, 5, 10, 15, 20, 25, y=20 or 14 and z=5 or 11 (mol%), has been prepared by melting raw materials in two parent glasses and performing heat treatments. The systematic substitution of BaO for CaO in the base glasses allows the effect of feldspars’ isomorphism and polymorphism to be studied in a series of glass-ceramics where the structural environment around the bivalent cations, Ca2+ and Ba2+, is systematically altered. Ba2+ has a large effect on the glass transition temperature and dilatometric softening point, causing a decrease with increasing BaO. The crystalline phases have been identified and found to be dependent on the preparation conditions, which are the BaO and Al2O3 contents, the heating rate and the soaking temperature adopted for the crystallization treatments. The infrared spectroscopy technique helped to identify the different polymorphs of barium feldspar, that were not clearly distinguishable by X-ray powder diffractometry due to preferred orientations. The kinetic parameters for the formation of the different crystals have also been determined and correlated with their thermal stability resumed in the well-known time-temperature-transformation curves.