The gas phase species produced in rf plasmas of hexamethyldisiloxane (HMDSO), Si2O(CH3)(6), diluted with oxygen, have been investigated. The complementarity of Fourier transform infrared absorption spectroscopy and mass spectrometry allows the determination of the most abundant neutral components present in the discharge. The measurements reveal that methyl groups (CH3), abundantly formed by the dissociation of the HMDSO molecule, are the precursor for the most abundant species which stem from two kinds of reaction. The first kind of reaction is combustion of CH3 by oxygen-producing formaldehyde (COH2), formic acid (CO2H2), carbon monoxide (CO), carbon dioxide (CO2) and water. It is shown that high mass carbonated radicals, such as SixOyCzHt, first diffuse to the surface and then the carbon is removed by oxygen etching to form CO2. The second is hydrocarbon chemistry promoted by CH3, producing mainly hydrogen (H-2), methane (CH4) and acetylene (C2H2).