Abstract Affected by environmental states and power supply parameters, the discharge mode of surface dielectric barrier discharge plasma may gradually transfer from O3 mode to NOx mode, resulting in various gas-phase species for different applications. Despite the intensive study of attempts to control this discharge mode transition by changing discharge conditions and power excitations in recent years, the effects of the pulse rise time and the pulse width on the discharge mode transition have not been discussed. In the present study, a surface dielectric barrier discharge was excited by repetitive pulses with different pulse rise times or pulse widths, and the time-varying concentrations of key long-lived species (O3 and NO2) were quantified. The results demonstrated that it was possible to modulate the discharge mode by adjusting pulse rise time/pulse width. The quenching of O3 was observed to occur at a faster rate and the mode transition was noted to occur at an earlier point in time as the pulse rise time decreased from 225 ns to 125 ns and the pulse width increased from 0.5 μs to 4 μs. The employment of a zero-dimensional model for the analysis of plasma chemical kinetics revealed that the reduction in pulse rise time and the prolongation of pulse width resulted in an increase in the mean vibrational energy of N2(v) and a more rapid electrode temperature rise caused by plasma heating. The former enhanced the generation of NO, while the latter accelerated the thermal decomposition of O3, thereby promoting the speed of mode transition.