Brownmillerite-type Sr 2 ScGaO 5 has been investigated by a range of experimental X-ray and neutron scattering techniques (diffraction, total scattering, and spectroscopy) and density functional theory calculations in order to characterize its structure and dynamics. The material undergoes a second-order phase transition on heating during which a rearrangement of the (GaO 4/2) ∞ tetrahedral chains occurs, such that they change from being essentially fully ordered in a polar structure at room temperature to being orientationally disordered above 400°C. Pair distribution function analysis carried out using neutron total scattering data suggests that GaO 4 tetrahedra remain as fairly rigid units above and below this transition, whereas coordination polyhedra in the (ScO 6/2) ∞ layers distort more. Inelastic neutron scattering and phonon calculations reveal the particular modes that are associated with this structural change, which may assist ionic conductivity in the material at higher temperatures. On the basis of the correlations between these findings and the measured conductivity, we have synthesized a derivative compound with increased conductivity and suggest a possible conduction mechanism in these brownmillerite-type solid electrolytes.