X-ray diffraction technique using a laboratory radiation has generally shown limitation in detectability. In this work, we investigated the in situ high-temperature crystallization of a lithium disilicate glass-ceramic in the SiO 2–Li 2O–CaO–P 2O 5–ZrO 2 system with the aid of synchrotron radiation. The formation of lithium metasilicate and other intermediate phases in trace amount was successfully observed by synchrotron X-ray diffraction (SXRD). The crystallization mechanism in this glass was thus intrinsically revised to be the co-nucleation of lithium metasilicate and disilicate, instead of the nucleation of lithium disilicate only. The phase content, crystallite size and crystallographic evolutions of Li 2Si 2O 5 in the glass-ceramic as a function of annealing temperature were studied by performing Rietveld refinements. It is found that the growth of Li 2Si 2O 5 is constrained by Li 2SiO 3 phase at 580–700°C. The relationship between the crystallographic evolution and phase transition was discussed, suggesting a common phenomenon of structural response of Li 2Si 2O 5 along its c axis to other silicon-related phases during glass crystallization.