This study analyzes the selective productions of nitrogen oxides and ozone in dielectric barrier discharge due to temperature controlled by the dual duty cycle. In this work, we varied the dual duty cycle of the output voltage in the power supply, which alternatively generates distinguished high and low‐temperature modes for selective productions of nitrogen oxides and ozone. The alternating nitric oxide and ozone by dual duty cycle were measured at a maximum of 100 ppm and 100 ppm in the gas phase, respectively. In the evaluation of DI water treated by dual duty cycle, nitrogen oxides, and ozone have been observed simultaneously in the liquid phase. These results offer new insights into the selective production of temperature‐dependent chemical characteristics for advanced plasma applications.