A detailed investigation of the overall crystal structure, and in particular of the local structure around the cations in M2La3Sb3O14 (M = Mg, Ca) was accomplished using X-ray diffraction, steady state luminescence spectroscopy and decay kinetics, and state of the art density functional calculations. The computational tool was also used to investigate the structure of Mn2La3Sb3O14. The Eu3+ dopant ion was employed as an optical probe of the local symmetry at the cationic sites. The use of these complementary techniques shows that the antimonates under investigation belong to the rhombohedral pyrochlore family with space group R<(3)overbar>m (No. 166), but while Mg2La3Sb3O14 and Mn2La3Sb3O14 show an ordered cationic configuration, the Ca2+ and La3+ of Ca2La3Sb3O14 are disordered because of their similar ionic radii. In both the Mg- and the Ca-based compounds, the Eu3+ ions formally occupy centrosymmetric sites, but in the case of Ca2La3Sb3O14 the presence of disorder in the outer coordination spheres removes the local inversion symmetry in these sites. This has a strong influence on the Eu3+ luminescence spectrum and on the radiative decay rate of the D-5(0) emitting level.