The distribution of Cr3+ ions in blue and green diopsides crystallised from a glass with the composition [CaMgSi2O6 (Di)]95[CaCrAlSiO6 (CrAlTs)]5 (mol.%) was determined using Rietveld refinement of X-ray diffraction data in order to evaluate published results by optical spectroscopic analysis, and to clarify the influence of Cr3+–Al3+ distribution between the octahedral M1 and tetrahedral T sites on the crystal structure. The starting material was Di95CrAlTs5-diopside crystallised from glass at 800°C for 2 days. After another 19 days at 800°C and 1000°C for 7 days, the diopsides remained blue. The blue diopside gradually changed to bluish green by heating at 1200°C for 3 days and to green after 7 days. The stoichiometric compositions of the synthesised phases were confirmed by electron microprobe analysis. The Cr occupancies refined by the Rietveld method resulted in the site populations in the M1 and T sites: M1[Mg0.95Cr0.030(4)Al0.020]T[Si1.950Cr0.020Al0.030] and M1[Mg0.95Cr0.037(4)Al0.013]T[Si1.950Cr0.013Al0.037] (per 6 oxygens) for the blue diopsides at 800 and 1000°C, respectively: M1[Mg0.95Cr0.042(3)Al0.008]T[Si1.950Cr0.008Al0.042] for the bluish green diopside at 1200°C for 3 days; and M1[Mg0.95Cr0.049(3)Al0.001]T[Si1.950Cr0.001Al0.049] for the green diopside at 1200°C for 7 days. Such Cr and Al distributions effect the volumes and site distortions of the octahedral and tetrahedral coordination polyhedra: the TO4 tetrahedron volumes of the blue diopsides (2.251–2.258 Å3) are larger than that of the green diopside (2.237 Å3); the M1O6 octahedron volumes of the former (11.74–11.77 Å3) are smaller than that of the latter (11.86 Å3); the TO4 tetrahedra in the blue diopside (<λtet> =1.006; σθ(tet)2 = 24.37–24.69) are less distorted than that of the green diopside (<λtet> = 1.007; σθ(tet)2 = 27.94); the M1O6 octahedra in the former (<λoct> =1.006; σθ(oct)2 = 20.39–21.13) are more distorted than that of the latter (<λoct> = 1.005; σθ(oct)2 = 17.58).