Annealing effect of amorphous carbon thin films on Si(1 0 0) substrates is studied by normal incidence and angle dependent carbon K-edge X-ray absorption near-edge structure (XANES) spectroscopy. The angle dependence of the XANES signal shows that the graphitic basal planes are oriented perpendicular to the surface when the film is annealed at 1000 °C. Micro-Raman spectroscopy reveals two well-separated bands the D band at 1355 cm−1 and G band at ∼1600 cm−1, and their ID/IG intensity ratio indicates the formation of more graphitic film at higher annealing temperatures. X-ray diffraction pattern of 1000 °C temperature annealed film confirms the formation of graphite structure.