The bonding of Si atoms in μc-Si:H thin films has been investigated using X-ray photoelectron spectroscopy (XPS) in conjunction with infra-red spectroscopy (IR), secondary ion mass spectroscopy (SIMS) and analytical electron microscopy (TEM/EDX/EELS) data. By using a-Si:H and single crystal silicon as reference samples, structural and hydrogen effects could be assessed, since both a-Si:H and μc-Si:H have a similar concentration of hydrogen based on the N15 hydrogen profiling data, but different structures. On the other hand, single crystal silicon and μc-Si:H both have a diamond cubic structure based on electron diffraction data, but single crystal silicon contains little or no hydrogen except adsorbed at the surface. Based on the XPS and IR data, charge transfer of the Si2p core level towards a deep lying level was observed in the μc-Si:H material. IR measurements snowed a large amount of hydrogen was located in the grain boundaries. The charge transfer is mainly due to a change in the hydrogen bonding configuration. A well bonded oxide is formed in the μc-Si:H material near the surface with an almost complete absence of the Si3+ intermediate oxide state. The presence of a large amount of hydrogen (25 at.%) even at a high volume fraction (70%) of μc-phase may limit the oxidation and promote better oxide formation. The variation of the quality of the oxide/μc interface could be a possible explanation for the different photoluminescence observed by various groups for porous μc-Si material.