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With the aim of extracting information on the electronic structure of carbon-based materials, double-differentiated C KVV Auger lines of graphite, diamond and different amorphous carbon (a-C) samples have been obtained using the XAES (X-ray excited Auger electron spectroscopy) technique. Comparison with theory and data taken from other experimental methods has shown that the structures found in the second-derivative Auger C KVV spectra can be satisfactorily explained, to first approximation, in the frame of a simplified Auger transitions model and that they reflect the behaviour of the occupied DOS (density of states) of the material under study. The second-derivative C KVV Auger analysis was shown to be very surface sensitive and able to deliver simultaneous information about p- and s-bonding character in the valence band electronic structure otherwise not obtainable with common photoemission techniques like UPS (ultraviolet photoelectron spectroscopy) and XPS (X-ray photoelectron spectroscopy).