Yttria partially stabilized zirconia Y-PSZ/glass-ceramic composites were prepared by reaction sintering using powder mixtures of a SiO2–Al2O3–ZnO–CaO–ZrO2–TiO2-based glass and yttria partially stabilized zirconia (Y-PSZ). The glass crystallized during sintering at temperatures of 1173, 1273, and 1373 K to give a glass-ceramic matrix for high-temperature protecting coatings. With the increasing firing time, the added zirconia reacted with the base glass and a glass-ceramic material with dispersed zircon particles was prepared in situ. Furthermore, the added zirconia changed the crystallization behavior of the base glass, affecting the shape, amount, and distribution of zircon in the microstructure. The bipyramid-like zircon grains with imbedded residual zirconia particles turned out to have two growth mechanisms: the inward growth and the outward growth, and its rapid growth was mainly dominated by the later one. For comparison, the referenced glass-ceramic was prepared by sintering using exclusive glass granules and its crystallization behavior at 1173–1373 K was examined as well. Scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM), and X-ray diffraction (XRD) were used to characterize the crystallization behavior of the base glass and the phase evolution of the Y-PSZ/glass-ceramic composites.