Electronic and bonding properties of Me-based hydrogenated amorphous carbon (a-CH:Me, Me = Fe, Ni) thin films have been studied by X-ray absorption near-edge structure (XANES), valence-band photoemission (VB-PES) and Raman spectroscopy. Raman and XANES results show enhancement of the content of sp3-rich diamond-like carbon (DLC) by doping with Fe and Ni. The VB-PES spectrum of a-CH:Fe shows emergence of a prominent feature due to states of sp3-bonded clusters, indicating that a-CH:Fe induced enhancement of DLC structure. The nano-indentation measurement reveals that a-CH:Fe has a greatly enhanced hardness, while electrical resistance measurement shows that a-CH:Me reduces resistivity.