Three perovskites with the general formula La 0.75 Ba x Sr 0.25−x Cr 0.5 Mn 0.5 O 3 (x = 0, 0.10 and 0.25) have been synthesized. For all materials, the symmetry is rhombohedral (space group R-3c). On the electrical point of view, a p-type semiconducting behaviour was evidenced in the series. The addition of barium yields an increase in total conductivity in argon from 18 S cm −1 for La 0.75 Sr 0.25 Cr 0.5 Mn 0.5 O 3 to 26 S cm −1 for La 0.75 Ba 0.25 Cr 0.5 Mn 0.5 O 3 at 900 °C. However, in H 2 –3% H 2 O, the total conductivity decreases for all compositions and it decreases with barium substitution (0.9 S cm −1 for La 0.75 Sr 0.25 Cr 0.5 Mn 0.5 O 3 and 0.5 S cm −1 for La 0.75 Ba 0.25 Cr 0.5 Mn 0.5 O 3 at 900 °C). Steady state and impedance spectroscopy measurements were performed on dense pin-shaped electrodes (x = 0 and 0.25) in H 2 –3% H 2 O between 800 and 900 °C. For x = 0.25, electrochemical performances are interesting for an applicability as an SOFC anode. Origins of individual contributions to the electrode reaction mechanism are discussed.