AbstractWe analyze in this work the influence of ordering on the oxygen ion dynamics in the ionic conductor Gd₂(Ti_0.65Zr_0.35)₂O₇, prepared by mechanical milling. As-prepared powder phase presents a metastable anion deficient fluorite-type of structure below 800°C becoming a disordered pyrochlore above this temperature. Such phase transformation implies a significant increase in the ionic conductivity of this material as a result of a systematic decrease in the activation energy for the dc conductivity, from 1.23 to 0.78 eV. Electrical conductivity relaxation is well described by the Kohlrausch-Williams-Watts (KWW) stretched exponential function with the fractional exponent n decreasing systematically with increasing sintering temperature (increasing ordering) as a result of decreasing ion-ion interactions in better ordered samples.