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The C KLL spectra from natural diamond, graphite, and single‐crystal β‐SiC have been investigated using x‐ray photoelectron spectroscopy and first‐derivative x‐ray excited Auger electron spectroscopy (XAES). It is shown that the XAES spectra is essentially the same as that obtained with conventional AES with the added benefits of no electron beam (e‐beam) damage, enhanced fine structure, and the simultaneous acquisition of the C 1s and valence‐band spectra. The C KLL XAES fine structure provides a fingerprint of the carbon bonding state and the C 1s and valence‐band spectra provide insight into the origin of this fine structure. Diamondlike carbon films fabricated by hydrogen gas reactive sputtering of graphite on Si were also investigated. The XAES C KLL spectra in conjunction with the valence‐band spectra verifies the tetrahedral C–C bonding in these films even though the AES spectra shows a graphitelike structure; indicative of e‐beam damage.