The atomic bonding configuration of ultrananocrystalline diamond (UNCD)/hydrogenated amorphous carbon (a-C:H) films prepared by pulsed laser ablation of graphite in a hydrogen atmosphere was examined by near-edge X-ray absorption fine structure spectroscopy. The measured spectra were decomposed with simple component spectra, and they were analyzed in detail. As compared to the a-C:H films deposited at room substrate-temperature, the UNCD/a-C:H and nonhydrogenated amorphous carbon (a-C) films deposited at a substrate-temperature of exhibited enhanced and peaks. At the elevated substrate-temperature, the and bonds formation is enhanced while the C–H and C–C bonds formation is suppressed. The UNCD/a-C:H film showed a larger C–C peak than the a-C film deposited at the same elevated substrate-temperature in vacuum. We believe that the intense C–C peak is evidently responsible for UNCD crystallites existence in the film.