Cation ordering in the magnesioferrite-qandilite (MgFe2O4-Mg2TiO4) solid solution has been investigated using an interatomic potential model combined with Monte Carlo simulations. The dominant chemical interaction controlling the thermodynamic mixing behavior of the solid solution is a positive nearest-neighbor pairwise interaction between tetrahedrally coordinated Fe3+ and octahedrally coordinated Ti4+ (JTFeOTi). The predicted cation distribution evolves gradually from the Néel-Chevalier model to the Akimoto model as a function of increasing JTFeOTi, with JTFeOTi = 1000 ± 100 K providing an adequate description of both the temperature and composition dependence of the cation distribution and the presence of a miscibility gap. Although Mg is a good analog of Fe2+ in end-member spinels, a comparison of model predictions for MgFe2O4-Mg2TiO4 with observed cation ordering behavior in titanomagnetite (Fe3O4-Fe2TiO4) demonstrates that the analog breaks down for Fe3O4-rich compositions, where a value of JTFeOTi closer to zero is needed to explain the observed cation distribution. It is proposed that screening of Ti4+ by mobile charge carriers on the octahedral sublattice is responsible for the dramatic reduction in JTFeOTi. If confirmed, this conclusion will have significant implications for attempts to create a realistic thermodynamic model of titanomagnetite.