Cr2O3 is a common nucleating agent useful for forming ceramics from oxide glasses. In this study we have used a variety of synchrotron radiation techniques to examine the atomic structure, crystallinity and microstructure of a magnesium alumino-silicate glass ceramic whose composition is close to that of the mineral cordierite, Mg2Al4Si5O13. X-ray Absorption spectra on the Cr K-edge have been performed with samples that were heat treated at different temperatures and times to examine the metamorphosis of the nucleating site. This study reveals that Cr3+ is always octahedrally coordinated with oxygen. In addition, the second nearest neighbour environment changes from an amorphous, single shell of Al/Si, but upon crystallisation, develops into a well ordered Al/Mg shell indicative of the formation of a dilute Cr spinel phase. Powder X-ray Diffraction (XRD) patterns, however, reveal that the major phase initially precipitated (˜900°C) is a stuffed quartz and from the lattice parameters that the composition is SiO2 -rich. With prolonged heat treatment a small quantity of a spinel phase emerges whose composition from its lattice parameter is close to MgAl2O4. Combined Small Angle X-ray Scattering (SAXS) and XRD establish that devitrification at these temperatures is associated with particles about 250 Å in size, on average. Energy dispersive powder diffraction patterns were collected in situ to observe changes in crystallinity with temperature and time. From these measurements the stuffed quartz phase identified at 900°C is found to be intermediate, being eventually replaced at higher temperatures by cordierite with a small quantity of spinel.