Yttrium-doped barium zirconate protonic conductors were synthesized by a two-step route consisting on diffusing barium ions into previously prepared yttrium-doped zirconia. The evolution of the structural phase content was followed by in situ high temperature X-ray diffraction in the room temperature-1200°C and by X-ray diffraction analysis of a mixture of cubic yttria-stabilized zirconia and barium carbonate heat treated at high temperatures. The attainment of the BaZr 0.85 Y 0.15 O 3-δ composition was evaluated by X-ray fluorescence measurements. Pellets sintered at 1500°C had the electrical behavior under humidified argon studied by impedance spectroscopy in the 300-600°C in the 40 Hz-110 MHz frequency range. Unitary planar solid oxide fuel cells La 0.6 Sr 0.4 Fe 0.8 Co 0.2 O 3 /BaZr 0.85 Y 0.15 O 3-δ /Pt were assembled for measuring the output voltage under operation with hydrogen, methane and ethanol as fuels and air as the oxidant.