A plasma's working gas is a significant factor affecting their discharge characteristics and the induced chemistries during plasma–water interactions. However, the effects on the discharge mode and discharge stability have not been fully investigated. This study focuses on the discharge mode transition and stability with nitrogen and oxygen gases. Compared with the oxygen discharge, the nitrogen discharge remained stable over a larger voltage range and long duration time. A diffuse mode discharge had better stability and lower plasma activity for both nitrogen and oxygen gases, whereas a transient spark mode in nitrogen and filament mode in oxygen had lower stability but a higher plasma activity. This study improves the understanding of the physicochemical processes of plasma–water interactions.