The results of the synthesis and characterisation of pyrochlore systems Sm1.92Ca0.08Ti2O7-delta and Sm2Ti1.92Y0.08O7-delta are reported. The electrical conductivity of the materials was studied using impedance spectroscopy under wet and dry oxygen and argon. Enhancements of the bulk conductivity at temperatures up to 500 degrees C were observed for wet conditions indicative of significant proton conductivity. The presence of dissolved protons in the materials is supported by thermogravimetric analysis and infrared spectroscopy. Proton conduction was confirmed by measurements in O-2/D2O and Ar/D2O. The results reveal the importance of the correct choice of dopant site for the pyrochlore structure, with A-site substitution yielding the highest levels of proton, as well as oxide ion, conduction. For both samples bulk, rather than grain boundary, conduction is found to be dominant. (C) 2009 Elsevier BM. All rights reserved.