Barium hollandites, a family of framework titanates that can potentially be used for the immobilization of short-lived fission products (especially 137Cs) in radioactive wastes, have been investigated by high-temperature oxide melt solution calorimetry using 2PbO·B2O3 solvent at 702°C. The enthalpies of formation from constituent oxides show increasing energetic stability of the hollandite phase as Ti4+ is substituted by Mg2+, Al3+, and Fe3+, in that order. In general, the thermodynamic stability increases with decreasing average cation radius in the β sites, and when the tolerance factor approaches one. The Al- and Fe-hollandites are more stable than phase assemblages containing BaTiO3 perovskite and Al/Fe/Ti oxides, whereas Mg-hollandite is less stable than the corresponding assemblage of BaTiO3 perovskite, MgTiO3 ilmenite, and TiO2. This instability makes Mg-hollandite a less suitable host for fission products. Hollandite phase formation during metal citrate combustion synthesis depends more on thermodynamic stability and phase chemistry than on the annealing temperature.