We report a facile route for the preparation of polyphenylsiloxane ((1 - x)PhSiO3/2-(x)Ph2SiO2/2 (x = 0, 0.1, 0.2, 0.3)) glass films from 50 to 150 mu m thick. The films were obtained via a multi-step spin-coating process at room temperature using a nonaqueous coating sol where the preformed polyphenylsiloxane is homogeneously dissolved in acetone. The different stages of the spinning process have been described and optimised, and represent an important issue to the preparation of homogeneous films. The thickness of the films (H) coated on silica and polyethyleneterephtalate substrates showed a trend dependency with the so] viscosity (eta), H proportional to eta(0.37) and H proportional to eta(0.41), respectively, making the thickness of the films easy to control. The average surface roughness evaluated to be less than 5 nm and the high optical transmittance (99%) demonstrated the high quality coatings. In addition, the stability of the glass matrix in the solvent makes this method of practical interest for tremendous possibilities in a wide range of applications such as the development microfluidic channels, protective coatings and optical components. (C) 2006 Elsevier Ltd. All rights reserved.