Crystallization behavior of various compositions of MgAl2O4 –SiO2 glasses was investigated. Glasses with chemical compositions from MgAl2O4/SiO2 = 1/1 to 1/8, spanning the range of cordierite composition (1:2.5) were prepared by a rapid quenching method using an arc image furnace and twin roller. During thermal treatment, all the glasses first crystallized to form high-quartz solid solution (HQss), then transformed to high-cordierite at higher temperature. Transformation from high-cordierite to low-cordierite required prolonged firing times even at high temperature. The crystallization temperature of HQss and the transformation temperature from HQss to high-cordierite changed only slightly in the glasses with MgAl2O4/SiO2 ratios greater than cordierite composition, whereas large increases were found for glasses with MgAl2O4/SiO2 ratios lower than cordierite. The HQss phase appeared in the samples spanning a wide MgAl2O4/SiO2 range and showed superlattice reflections which doubled the fundamental lattice parameters. The cause for HQss formation prior to the appearance of cordierite in these glass samples is discussed from a structural viewpoint involving ordering-disordering of SiO4 and AlO4 tetrahedra deduced from 29Si and 27Al MAS-NMR spectra.