In this study, we employed a nanosecond‐pulsed gear‐cylinder dielectric barrier discharge (DBD) assisted by a perpendicular magnetic field (MF) for toluene degradation. The effects of key discharge and gas parameters, as well as their optimal combinations with the perpendicular MF, on toluene degradation were systematically investigated. The results indicated that the maximum toluene degradation efficiency was achieved under conditions of short pulse rising times and widths, low gas flow velocities, and minimal oxygen concentrations. This optimal performance was attributed to three main factors: high mean electron energy, the generation of appropriate active oxygen species, and an extended residence time for plasma‐toluene molecule interactions. Furthermore, by meticulously adjusting the operational parameters, augmenting the number of magnetized energetic electrons in the perpendicular MF, and intensifying the ionization process, we observed a notable enhancement in both discharge intensity and toluene degradation efficiency.