Three perovskites with the general formula La0.75BaxSr0.25-xCr0.5Mn0.5O3 (x = 0, 0.10 and 0.25) have been synthesized. For all materials, the symmetry is rhombohedral (space group R-3c). A p-type semiconducting behaviour was evidenced. In comparison to La0.75Sr0.25Cr0.5Mn0.5O3, the total conductivity of barium containing compounds is higher in argon and it is nearly independent of barium content in humidified hydrogen above 700C. Steady state and impedance spectroscopy measurements were performed on dense pin-shaped electrodes (x = 0 and 0.25) in H2-3% H2O between 800 and 900C. For x = 0.25, anodic performances are interesting for an applicability as a SOFC anode. Origins of individual contributions to the electrode reaction mechanism are discussed.