The reducibility of oxide-ion conductors La2-xBaxMo2-yWyO9-δ(x = 0, 0.06; y = 0, 0.1) were studied in the reducing atmosphere of 5%H2 + Ar by means of impedance spectroscopy measurement.. All substitutions can enhance the conductivity and improve the reducibility in the temperature range from 548 to 923 K. The double substitution of Ba and W has a better stabilizing effect than the single tungsten substitution.