Phase transition points can be used to critically reduce the ionic migration activation energy, which is important for realizing high-performance electrolytes at low temperatures. Here, we demonstrate a route toward low-temperature thermionic conduction in solids, by exploiting the critically lowered activation energy associated with oxygen transport in Ca-substituted bismuth ferrite (Bi1-xCaxFeO3-delta) films. Our demonstration relies on the finding that a compositional phase transition occurs by varying Ca doping ratio across x(Ca) similar or equal to 0.45 between two structural phases with oxygen-vacancy channel ordering along or crystal axis, respectively. Regardless of the atomic-scale irregularity in defect distribution at the doping ratio, the activation energy is largely suppressed to 0.43 eV, compared with similar to 0.9 eV measured in otherwise rigid phases. From first-principles calculations, we propose that the effective short-range attraction between two positively charged oxygen vacancies sharing lattice deformation not only forms the defect orders but also suppresses the activation energy through concerted hopping. Phase transition points can be used to reduce the ionic migration activation energy. Here, the authors find a lowered activation energy associated with oxygen transport at a compositional phase transition point in Ca-doped bismuth ferrite films.