In this work we report on the microwave assisted synthesis of nano-sized Gd₂Ti₂O₇ (GTO) and Ho₂Ti₂O₇ (HTO) powders from the RE₂Ti₂O₇ pyrochlore family (RE = rare earth). Synchrotron X-ray powder diffraction was used to study RE–Ti cationic anti-site defects with concentrations that decrease in both samples with increasing temperature starting from 1100 °C, and the defects disappear at 1400 °C. SQUID magnetometry measurements revealed that GTO shows a predominantly anti-ferromagnetic structure, whereas HTO exhibits magnetic saturation and a ferromagnetic component at low temperature. Impedance spectroscopy data revealed strongly increased ionic oxygen vacancy conduction in HTO ceramic pellets as compared to GTO, which may be associated with a higher degree of oxygen vacancy disorder. This argument was supported by Raman spectroscopy data.