Silicon carbide (SiC) is an important material for several applications ranging from electronics to Extreme UltraViolet (EUV) space optics. Crystalline cubic SiC (3C–SiC) has a wide band gap (near 2.4eV) and it is a promising material to be used in high frequency and high energetic electronic devices. We have deposited, by means of pulsed laser deposition (PLD), different SiC films on sapphire and silicon substrates both at mild (650°C) and at room temperature. The resulted films have different structures such as: highly oriented polycrystalline, polycrystalline and amorphous which have been studied by means of X-ray absorption spectroscopy (XAS) near the Si L 2,3 edge and the C K edge using PES (photoemission spectroscopy) for the analysis of the valence bands structure and film composition. The samples obtained by PLD have shown different spectra among the grown films, some of them showing typical 3C–SiC absorption structure, but also the presence of some Si–Si and graphitic bonds.