While interfacial graphite formation and subsequent poor film adhesion is commonly reported for chemical vapor deposited hard carbon films on cobalt-based materials, we find the presence of O 2 in the feedgas mixture to be useful in achieving adhesion on a CoCrMo alloy. Nucleation studies of surface structure before formation of fully coalesced hard carbon films reveal that O 2 feedgas helps mask the catalytic effect of cobalt with carbon through early formation of chromium oxides and carbides. The chromium oxides, in particular, act as a diffusion barrier to cobalt, minimizing its migration to the surface where it would otherwise interact deleteriously with carbon to form graphite. When O 2 is not used, graphitic soot forms and films delaminate readily upon cooling to room temperature. Continuous 1 μm-thick nanostructured carbon films grown with O 2 remain adhered with measured hardness of 60 GPa and show stable, non-catastrophic circumferential micro-cracks near the edges of indent craters made using Rockwell indentation. © 2010 Springer Science+Business Media, LLC.