This research explores the potential of electric field enforcement in dielectric barrier discharge using specially designed pyramid‐shaped μ‐electrodes for a plasma‐assisted nitrogen fixation process. The obtained results are compared under varying conditions, including the presence and absence of titanium dioxide (
), different oxygen concentrations in the nitrogen‐feeding gas, and residence time. The results demonstrate that the μ‐electrodes lead to an enhancement of nitrogen oxidation, which is further intensified by
. The introduction of 60–70 % oxygen with nitrogen achieves the highest level of
production. The synergistic effect of plasma and the catalytic effect of
increase the rate of
production by 20 %, resulting in a 23 % increase in energy yield. The introduction of
leads to a sharp increase in
production even at lower oxygen concentrations. The crucial role played by ultraviolet light‐induced electron‐hole pairs in
is highlighted to promote nitrogen oxidation. Nevertheless, it is crucial to emphasize that prolonged residence times may cause the photocatalytic effect to generate alternative byproducts rather than
, consequence of excessive oxidation that could prove counterproductive. These findings emphasize the potential of plasma‐assisted nitrogen fixation technology in reducing energy costs and meeting the growing demand for sustainable nitrogen‐based fertilizers.