To improve NO oxidation and energy efficiency, the effect of dielectric barrier discharge reactor structure on NO oxidation was studied experimentally in simulated diesel exhaust at atmospheric pressure. The mixture of 15% O2/N2 (balance)/860 ppm NOX (92% NO + 8% NO2) was used as simulated diesel exhaust. The results show that DBD reactor with 100-mm electrode length has the highest oxidation degree of NOX and energy efficiency. NO oxidation efficiency is promoted and the generation of NO is inhibited significantly by increasing the inner electrode diameter. Increasing the inner electrode diameter not only improve the E/N, but also makes the distribution of E/N more concentrated in the gas gap. The secondary electron emission coefficient (γ) of electrode material is closely related to electron energy and cannot be considered as a constant, which causes the different performance of electrode material for NO oxidation under different gas gap conditions. Compared with the rod electrode, the screw electrode has a higher electric field strength near the top of the screw, which promotes the generation of N radicals and inhibits the generation of O radicals. Rod electrode has a higher NO oxidation and energy efficiency than screw electrode under oxygen-enriched condition.