Thin films were deposited from hexamethyldisiloxane (HMDSO) in a glow discharge supplied with radiofrequency (rf) power. Actinometric optical emission spectroscopy was used to follow trends in the plasma concentrations of the species SiH (414.2 nm), CH (431.4 nm), CO (520.0 nm), and H (656.3 nm) as a function of the applied rf power (range 5 to 35 W). Transmission infrared spectroscopy (IRS) was employed to characterize the molecular structure of the polymer, showing the presence of Si-H, Si-O-Si, Si-O-C and C-H groups. The deposition rate, determined by optical interferometry, ranged from 60 to 130 nm/min. Optical properties were determined from transmission ultraviolet-visible spectroscopy (UVS) data. The absorption coefficient Ir, the refractive index n, and the optical gap E(04) of the polymer films were calculated as a function of the applied power. The refractive index at a photon energy of 1 eV varied from 1.45 to 1.55, depending on the rf power used for the deposition. The absorption coefficient showed an absorption edge similar to other non-crystalline materials, amorphous hydrogenated carbon, and semiconductors. For our samples, we define as an optical gap, the photon energy E, corresponding to the energy at an absorption of 10(4) cm(-1). The values of E(04) decreased from 5.3 to 4.6 as the rf power was increased from 5 to 35 W.