Perovskite-type mixed oxides LaCrO3 and Nd0.95CrO3 were synthesized by the polymerization complex method. The perovskites were characterized by different techniques aiming to evaluate the influence of the non-stoichiometry and the nature of site A on the catalytic properties for the POM reaction. The non-stoichiometry and A sites did not affect the methane conversion, but the selectivity. The methane conversion with the neodymium catalyst Nd0.95CrO3 (N95) was 34%, and of the mixed La0.95CrO3 (L95) catalyst 38%, under these conditions. The rate of the Nd0.95CrO3 (N95) perovskite was equal to 3.50 mol.g(-1).h(-1) at 700 degrees C, which suggests higher activity compared to cobaltate perovskites. Although the hydrogen selectivity was similar the selectivity to CO and CO2 were different. Catalysts did not suffer structure changes during the POM reaction and negligible deactivation. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.