Nitrous oxide (N2O) is considered the primary source of NOx in the atmosphere, and among several abatement processes, catalytic decomposition is the most promising. The thermal energy necessary for this reaction is generally provided from the external side of the reactor by burning fossil fuels. In the present work, in order to overcome the limits related to greenhouse gas emissions, high heat transfer resistance, and energy losses, a microwave-assisted N2O decomposition was studied, taking advantages of the microwave’s (MW) properties of assuring direct and selective heating. To this end, two microwave-susceptible silicon carbide (SiC) monoliths were layered with different nickel−cobalt−aluminum mixed oxides. Based on the results of several characterization analyses (SEM/EDX, BET, ultrasound washcoat adherence tests, Hg penetration technique, and TPR), the sample showing the most suitable characteristics for this process was reproduced in the appropriate size to perform specific MW-assisted catalytic activity tests. The results demonstrated that, by coupling this catalytic system with an opportunely designed microwave heated reactor, it is possible to reach total N2O conversion and selectivity of a highly concentrated N2O stream (50 vol%) at T = 550 °C, the same required in the conventionally heated process to remove N2O from a less concentrated gas stream (20 vol%).