The high-temperature structures and phase transitions of the cation-ordered manganite perovskites TbBaMn2O6 and YBaMn2O6 have been studied by powder neutron diffraction and differential scanning calorimetry. TbBaMn2O6 undergoes an unprecedented transition from a charge and antiferro-orbitally ordered phase to a charge and ferro-orbitally ordered structure at 94.5 °C, and the charge and orbital ordering melts at 200 °C. An orthorhombic Cmmm phase with rotational order of MnO6 octahedra is observed above the transition, and at 514 °C this transforms to the aristotype tetragonal P4∕mmm arrangement. YBaMn2O6 is charge and ferro-orbitally ordered up to 225 °C. Above this charge ordering transition, a C2∕m phase with two rotational orders is found. This transforms to the Cmmm structure at 437 °C. Discontinuities in volume and volume expansion, and a limited phase coexistence region are observed at the charge ordering transitions, whereas the other transitions are continuous.