A group of complex metal oxides, BiMeVO x , which a fraction ( x) of V in Bi 4V 2O 11 is replaced by foreign metal, has been reported to be oxide-ionic conductors. The various kinds of oxides in this group, Me = Cu ( x = 0.1), Zr ( x = 0.1), Ti ( x = 0.4), Nb ( x = 0.15) and Ta ( x = 0.15), were investigated for electrochemical characterization based on oxygen concentration battery. The powders of BiMeVO x , their structural phases to the high temperature phase (γ) of Bi 4V 2O 11, were obtained by calcining at 700–850 °C. Each sample was compacted into a disk, and installed into an oxygen concentration cell. The oxygen concentration cells using the resulting disks of BiMeVO x , especially Me = Cu, were found to work as an oxygen sensor fairly well at 700 °C: the number of reaction electrons ( n) associated with the reduction of O 2 was close to the theoretical one (4). With lowering operating temperature, however, the O 2-responding properties degraded rather quickly: it was far larger at 500 °C. Such degradation was confirmed to be owing to decrease the rate of electrode reactions through the measurement of Faraday efficiency of oxygen pumping current. As a result, the performances of the cells were found to depend very much on the kinds of electrode materials. The use of a perovskite-type oxide, La 0.6Sr 0.4Co 0.8Fe 0.2O 3, instead of Pt as a electrode was found to enable the cell to work at 400 °C and above.