Diamond-like carbon (DLC), a thin amorphous carbon film, has many uses in tribological systems. Exploiting alternative substrates and interlayers can enable the control of the hardness and modulus of the multilayer system and improve wear or friction properties. We used XPS and atomic force microscopy to examine DLC that had been concurrently coated on an epoxy interlayer and a steel substrate by plasma-enhanced chemical vapour deposition. sp 2/sp 3 ratios were calculated both by the deconvolution of the XPS C1s line and by the analysis of the C KLL Auger spectrum. Altering the substrate causes changes in the carbon bonding configuration, evident with the same trend through both analysis methods, although with differing absolute values, related to hydrogen and oxygen content. There is significant variation in the microscale surface texture, exhibited by both average roughness values and size and uniformity of surface asperities. This suggests that alteration to the film surface structure is a factor to be considered in addition to interface adhesion, hardness and elastic modulus in investigating substrates and interlayers for tribological coatings. Examination of a DLC film separately produced on a steel substrate, in comparison with that produced concurrently with a DLC coating on epoxy, shows the possibility of effects on the chemistry of the film through transfer of material from adjacent samples within the plasma deposition, related to heating, outgassing or sputtering processes. The possibility of such contamination has implications in coating parameter design and coating of multiple samples with plasma-enhanced chemical vapour deposition.