Potential applications of diamond-like carbon (DLC) coatings range from precision tools and biomedical implants to micro mechanical devices and engine components. Where uniform coatings are required on substrates with complex geometries, plasma enhanced chemical vapour deposition (PECVD) is often a preferred deposition method. As a non-line of sight process, the geometry of the substrate is often considered negligible. For this reason analysis of PECVD coatings, such as amorphous carbon, has mostly been concerned with reactor deposition variables, such as bias voltage, pressure and gas ratios. Samples are therefore usually prepared and positioned to minimise the influence of other variables. By depositing nominally similar DLC films on silicon samples positioned horizontally and vertically on the reactor cathode plate it was possible to examine the variations in the coating characteristics and mechanical properties that occur due to the geometry of the substrate being coated. Topographic measurements and analysis of bonding structures revealed significant heterogeneity in the coatings. Electron microscopy showed variation in surface structure as well as thickness disparities of up to 50% in the vertical sample. Atomic force microscopy showed roughness, Ra, varied from 0.37nm to 15.4nm between samples. Raman spectroscopy highlighted variations in the sp2/sp3 bonding ratios whilst micro wear tests demonstrated how these variations reduce the critical load performance. These effects are explained in terms of the deposition mechanisms involved and are related to variation in deposition species and geometrical field enhancements within the deposition chamber. Improved understanding of these local variations will aid in the optimisation of coatings for complex substrate geometries.