Abstract Oxygenated amorphous carbon nitride thin films (a-CN x O y ) were deposited by pulsed laser deposition of camphoric carbon (CC) target at various substrate temperatures (ST). The influence of ST on the bonding properties of a-CN x O y films was investigated. The nitrogen to carbon (N/C) atomic ratio and oxygen to carbon (O/C) atomic ratio, bonding state and microstructure of the deposited a-CN x O y films were characterized by X-ray photoelectron spectroscopy (XPS) and been confirmed using standard measurement techniques. The bonding states between the C and N, and C and O in the deposited films are found significantly influenced by the ST during deposition process. The N/C and O/C atomic ratio of the a-CN x O y films reached the maximum value at 400 °C. The XPS C 1s shows the bonding state of a-CN x O y films changes from diamond-like tetrahedral (sp 3) carbon and carbon (C–C) bonding to graphite-like trihedral (sp 2) C C bonding with the increase of ST. While, the XPS N 1s shows the sp 3 C–N bonds increases with higher rates compared with sp 2 C N bonds up to 400 °C, after which it decreases with higher ST. The C–N bonding of C–N, C N and C N were observed in the deposited a-CN x O y films.