The perovskite BaCe(0.9−x)ZrxY0.1O(3−ı) is prepared by solid-state reaction at 1400 ◦C and sintering at 1700 ◦C. It is characterised using X-ray diffraction, Raman spectroscopy and electrical measurements. A distortion fromthe cubic structure at roomtemperature is noticeable in the Raman spectra for 0.2 < x < 0.8, but not in the X-ray diffraction patterns. This work points out the rhombohedral nature of this distortion. Phase transitions are studied up to 600 ◦C. The direct current conductivity is measured as a function of oxygen partial pressure, and at a water vapour partial pressure of 0.015 atm. The total conductivity is resolved into an ionic and a p-type component using a fitting procedure appropriate to the assumed defect model. The first contribution is useful for estimating the proton transport number, while the value of the second one should not be too high not to deteriorate the electrodes performance.