Lanthanum orthoferrite powders were synthesized via one‐step hydrothermal reactions under mild conditions using microwave and conventional heating. The use of microwave irradiation during the synthesis allows one to obtain nanocrystalline LaFeO3 with a higher yield and reduced crystallite and particle size within a 16 times shorter duration (3 hours) at a lower temperature of 220°C as compared to the conventional heating. The catalytic decomposition of nitrous oxide was performed over both samples, it was shown that the sample obtained under microwave conditions demonstrates enhanced activity as a catalyst: N2O decomposes completely at 700°C over the catalyst formed at microwave conditions, while the comparative catalyst prepared by conventional heating reaches a lower conversion of only 60% at the same temperature and catalytic reaction conditions. The use of microwave irradiation during the hydrothermal synthesis results in smaller LaFeO3 particles with higher amount of oxygen on the surface and, as a consequence, a higher activity in N2O decomposition.