The crystal structures of the leucite analogues Cs2MgSi5O12, Cs2ZnSi5O12 and Rb2MgSi5O12 have been determined by synchrotron X-ray powder diffraction using Rietveld refinement in conjunction with 29Si MAS NMR spectroscopy. These leucites are framework structures with distinct tetrahedral sites (T sites) occupied by Si and a divalent cation (either Mg or Zn in these samples); there is also a monovalent extra-framework cation (either Cs or Rb in these samples). The refined crystal structures were based on the Pbca leucite structure of Cs2CdSi5O12, thus a framework with five ordered Si T sites and one ordered Cd T site was used as the starting model for refinement. 29Si MAS NMR shows five distinct Si T sites for Cs2MgSi5O12 and Rb2MgSi5O12, but six Si T sites for Cs2ZnSi5O12. The refined structures for Cs2MgSi5O12 and Rb2MgSi5O12 were determined with complete T-site ordering, but the refined structure for Cs2ZnSi5O12 was determined with partial disorder of Mg and Si over two of the T sites.