Silicon carbonitride (SiCxNy) materials, inspired by their outstanding multifunctional properties, are finding increasing applications in a variety of fields, including as next generation solar cells and hard coatings. Hydrogenated SiCxNy thin films, along with binary submatrices of stoichiometric SiC and SiN3 as a reference, were deposited using electron cyclotron resonance plasma-enhanced chemical vapor deposition. We described a comparative study of the effects of post-deposition thermal annealing, from 300 to 1200 A degrees C, on the evolution of hydrogen-rich a-SiC1.2N0.7:H-1.4 thin films. Concurrently, two featured annealing temperatures (500 and 900 A degrees C) were found to have the significant influence on the morphology, optical, and microstructural properties of the films. During annealing the amorphous phase of SiC1.2N0.7:H-1.4 thin films was fully maintained according to the transmission electron microscopy and X-ray diffraction analyses. The hydrogen density was quantitatively analyzed employing two different experimental techniques, elastic recoil detection and Fourier transform infrared spectroscopy, showing the associate annealing temperatures of hydrogen desorption, breaking of all hydrogen-terminated bonds, and depletion of all hydrogen content. The refractive indices and optical band gap of the films were calculated using variable angle spectroscopic ellipsometer. Thermal annealing resulted in hydrogen desorption and consequently layer densification along with an increase in the refractive index. During the annealing process, first the optical band gap widened, and then narrowed due to hydrogen out-diffusion or chemical bond restructuring, depending on the annealing temperature. In addition, Rutherford backscattering spectrometry and X-ray photoelectron spectroscopy were performed. These findings are discussed in the context of the interdependency of the hydrogen desorption and thermally induced changes in chemical bonds, mass density, and optical properties.