Reactive oxygen–nitrogen species (RONS) production in a Peltier-cooled hybrid dielectric barrier discharge (HDBD) reactor operated with humid air is characterized. Fourier-transform infrared spectroscopy (FTIR) is used to determine the RONS in the HDBD-produced gases. The presence of molecules ${\mathrm{O}}_3$, ${\mathrm{NO}}_2$, ${\mathrm{N}}_2$O, ${\mathrm{N}}_2{\mathrm{O}}_5$, and ${\mathrm{HNO}}_3$ is evaluated. The influence of HDBD reactor operation parameters on the FTIR result is discussed. The strongest influence of Peltier cooling on RONS chemistry is reached at conditions related to a high specific energy input (SEI): high voltage and duty cycle of plasma width modulation (PWM), and low gas flow. Both PWM and Peltier cooling can achieve a change in the chemistry from oxygen-based to nitrogen-based. ${\mathrm{N}}_2{\mathrm{O}}_5$ and ${\mathrm{HNO}}_3$ are detected at a low humidity of 7% in the reactor input air but not at humidity exceeding 90%. In addition to the FTIR analysis, the plasma-activated water (PAW) is investigated. PAW is produced by bubbling the HDBD plasma gas through 12.5 mL of distilled water in a closed-loop circulation at a high SEI. Despite the absence of ${\mathrm{N}}_2{\mathrm{O}}_5$ and ${\mathrm{HNO}}_3$ in the gas phase, the acidity of the PAW is increased. The pH value decreases on average by 0.12 per minute.