N2 oxidation to NOx is a challenging reaction, and alternative routes to the industrial Ostwald process are of interest. A perovskite under flowing O2-N2 mixtures at atmospheric pressure in a quartz tube reactor was irradiated by microwaves (MW), leading to the formation of hot spots and plasmas within the catalyst bed. NOx concentrations up to 2.5 vol.% in one pass were obtained at 600 W. Using a lower MW power of 100 W led to a pulsed mode yielding lower NOx concentrations and no noticeable damage to the quartz reactor. The formation of plasma was strongly dependent on the perovskite bed packing. The perovskite acted primarily as a susceptor and likely also as a catalyst, although the proportion of heterogeneous and homogenous reactions could not be determined in the present study. The simple reactor layout allowing operation at atmospheric pressure is promising for the development of practical MW-assisted N2 fixation technologies.