The electrical conductivities of Dion-Jacobson (D-J)-type layered perovskites ACa(2)Nb(3)O(10) (A = K, Rb, Cs) were investigated in the presence of different gas atmospheres. An increase in the electrical conductivity of about two to five orders of magnitude in both ammonia and hydrogen atmospheres as compared to air is observed in the investigated temperature regime 30-750 degreesC. Among the members studied, KCa2Nb3O10 exhibits the highest electrical conductivity with the lowest activation energy in hydrogen atmosphere. Open circuit voltage measurements using a hydrogen-air cell (H(2)parallel toair) reveal that as-prepared material exhibits mainly proton conductivity at low temperatures, while sample taken after the AC impedance measurements in hydrogen atmosphere and quenched to room temperature shows significant electronic contribution. The electrical conductivity changes as a function of the ammonia/hydrogen gas concentration. Accordingly, layered perovskites appear to be useful materials for practical applications (e.g., for gas sensors.) (C) 2004 Elsevier B.V. All rights reserved.