Surface properties of a large number of amorphous carbon (a-C) films have been investigated using contact angle measurements and X-ray photoelectron spectroscopy (XPS). Dense a-C surfaces with variable sp(3)/(sp(2) + sp(3)) average hybridization were grown using sputtering or pulsed laser deposition (PLD) and were further chemically modified by thermal annealing, ion bombardment or covalent grafting of organic monolayers. The average carbon hybridization, impurity level and mass density, were deduced from XPS and photoelectron energy loss spectroscopy ( PEELS). The depth sensitivity of the dispersive (Lifshitz-van der Waals) interaction, estimated at 1-2 nm from the dependence of gamma(LW) on the grafted perflorodecene molecule coverage, is much better than XPS which probes a 3-5 nm depth. The observation of a non-monotonic behavior in the correlation between surface hybridization and electron donor component of surface energy reveals that the average carbon hybridization alone does not describe the entire surface energy physics. The role of p bond clustering in the polar interactions is thus considered and some implications on surface reactivity and mutual interactions with molecular or biomolecular species are discussed. (C) 2008 Elsevier B.V. All rights reserved.