Using the techniques of reactive magnetron sputter deposition and inductively coupled plasma (ICP) assisted hybrid physical vapor deposition (PVD)/chemical vapor deposition (CVD), we have synthesized a wide variety of metal-free amorphous hydrocarbon (a-C:H) and Ti-containing hydrocarbon (Ti-C:H) coatings. Coating elastic modulus and hardness have been measured by the technique of instrumented nanoindentation and related to Ti and hydrogen compositions. We show that both metal and hydrogen compositions significantly influence the mechanical properties of Ti-C:H coatings. The microstructure of Ti-C:H coatings is further characterized by transmission electron microscopy (TEM), X-ray absorption near edge structure (XANES) spectroscopy, and extended X-ray absorption fine structure (EXAFS) spectroscopy. XANES spectroscopy and high-resolution TEM examination of Ti-C:H specimens shows that the dissolution limit of Ti atoms in an a-C:H matrix is between 0.9 and 2.5 at.%. Beyond the Ti dissolution limit, precipitation of nanocrystalline Bi-TiC cluster occurs and Ti-C:H coatings are in fact TiC/a-C:H thin film nanocomposites. Measurements of the average Ti bonding environment in TiC/a-C:H nanocomposites by EXAFS spectroscopy are consistent with a microstructure in which bulk-like Bi-TiC clusters are embedded in an a-C:H matrix.