Depending on the synthesis route, the oxygen ion electrolyte Sr2ScGaO5 shows two polymorphs, a brownmillerite and a cubic perovskite framework. In order to better explore oxygen diffusion pathways and mechanisms, we report here on a multitechnical approach to characterize local structural changes for Sr2ScGaO5 polymorphs as a function of temperature, using a neutron pair distribution function (PDF) analysis together with an extended X-ray absorption fine structure (EXAFS) analysis. While for the brownmillerite type structure PDF and Rietveld refinements yield identical structural descriptions, considerable differences are found for the cubic oxygen-deficient polymorph. On a local scale a brownmillerite type vacancy structure could be evidenced for the cubic phase, suggesting a complex short-range ordering and respective microstructure. Both PDF and EXAFS data confirm an octahedral and tetrahedral coordination for Sc and Ga, respectively, at a local scale for both polymorphs. Related changes in the bond distances and oxygen vacancy ordering are discussed.