Chemical and electrical characteristics of microcrystalline silicon films deposited from SiCl4 by an r.f. glow discharge were determined using X-ray photoelectron spectroscopy (XPS) and conductivity measurements. The chlorine content in the bulk was found to be about 2-3 at.%, forming partially ionic SiCl bonds as reflected by the XPS Cl2p chemical shift. The apparent shift in the Si 2p line is attributed to displacement of the Fermi level induced by the chlorine, which acts as a p-type dopant. This is confirmed by the electrical conductivity measurements carried out for undoped, B2H6- and PH3-doped films. The rather high dark conductivity σD ≈ 10-3 Ω-1 cm-1 of the undoped film seems to be associated with the microcrystalline structure. The degree and extent of silicon oxidation across the surface region were studied in detail for two differently air-exposed samples and are discussed in terms of the microcrystalline structure of the film. Compositional variations observed across the silicon-substrate interface are attributed to reactions with the stainless steel substrate during the initial deposition process.