In this study, silicon nitride (SiNx) thin films with different oxygen concentration (i.e., SiON film) were precisely deposited by plasma enhanced atomic layer deposition on Si (100) substrates. Thus, the effect of oxygen concentration on film properties is able to be comparatively studied and various valuable results are obtained. In detail, x-ray reflectivity, x-ray photoelectron spectroscopy, atomic force microscopy, and spectroscopic ellipsometry are used to systematically characterize the microstructural, optical, and electrical properties of SiON film. The experimental results indicate that the surface roughness increases from 0.13 to 0.2 nm as the oxygen concentration decreases. The refractive index of the SiON film reveals an increase from 1.55 to 1.86 with decreasing oxygen concentration. Accordingly, the band-gap energy of these films determined by oxygen 1s-peak analysis decreases from 6.2 to 4.8 eV. Moreover, the I-V tests demonstrate that the film exhibits lower leakage current and better insulation for higher oxygen concentration in film. These results indicate that oxygen affects microstructural, optical, and electrical properties of the prepared SiNx film.