Silicon-incorporated amorphous hydrocarbon (Si-aC:H) films with varying Si contents were deposited onto a Ti interlayer on Si and steel substrates by reactive sputtering in an unbalanced magnetron sputtering system. The objective of this study was to measure and relate the structural, chemical, and mechanical properties of these Si-aC:H films. Transmission electron microscopy revealed that the Si-aC:H phase is amorphous and TiC exists at the Si-aC:H/Ti phase boundary for all compositions. Mechanical properties such as hardness, indentation modulus, and intrinsic stress decreased with increasing Si and H content in the films, for Si/C ≥ 0.04. XPS measurements suggested that this is most likely due to the decreasing presence of a C-C sp3 interlinked network, accompanied by an increase in C-H and Si-H bonds. This conclusion was supported by radial distribution functions obtained using extended electron energy-loss fine structure analysis (EXELFS).