Coatings consisting of multilayer tungsten carbide/carbon (WC/C) were deposited by physical vapour deposition (PVD) onto steel substrates. The goal of this investigation was to probe the outcome of coatings dissimilarities as well as the substrate employed on the mechanical properties of the system by nanoindentation techniques. The coatings investigated are mainly composed of a chromium columnar interlayer to improve the adhesion to the substrate, an inter-multilayer of WC and carbon, and an interlaminar amorphous WC/C multilayer structure. The mechanical properties were assessed by nanoindentation techniques. The hysteresis loops were analysed and discussed in terms of the method developed by Oliver and Pharr. Moreover, a new technique for cross-sectional transmission electron microscopy of the nanoindentations has been developed, and the information obtained was correlated with the load–displacement data from a nanoindentation cycle to clarify the extent of any delamination fracture.