We investigated the effect of channel layer thickness (t ch ) on the electrical and thermal stabilities of high-mobility zinc oxynitride (ZnON) thin-film transistors (TFTs). ZnON TFTs with various t ch values of 11, 16, 21, and 26 nm were prepared for experiments. The drain current was barely modulated by the gate-to-source voltage in the ZnON TFT with a t ch of 26 nm. When t ch was less than 21 nm, both the electrical and thermal stabilities of the ZnON TFTs improved with an increase in t ch . To explain this phenomenon, the chemical composition and bonding states of the ZnON thin-films with different thicknesses were characterized using X-ray photoelectron spectroscopy (XPS). The XPS results indicated that more oxygen exists in the bulk of the 11-nm-thick ZnON thin-film than in the bulk of the 21-nm-thick ZnON thin-film. In addition, the number of defective Zn X N Y bonds decreased in the ZnON with an increase in the distance from the back surface to the characterized layer. Because the excess oxygen and defective Zn X N Y bond generate subgap states in ZnON, the observed t ch -dependence of the electrical/thermal stability in the ZnON TFT could be mainly attributed to the decrease in the subgap states in ZnON with the increase in t ch .