Solventless deposition of thin, uniform dielectric films is of considerable interest and importance in the microelectronics industry due to environmental concerns and increasing wafer sizes. This work demonstrates a solvent-free method for atmospheric pressure chemical vapor deposition polymerization of thin films on a variety of-substrates, including silicon, molybdenum, platinum and copper. Polymerization of 4-fluorostyrene (4FS) and pentafluorostyrene (PFS) is used as a model system. Depth profiling is performed using x-ray photoelectron spectroscopy, ellipsometry, and step profilometry. Film growth is found to be independent of substrate, and proceeds with activation energies of 14+/-1 and 15+/-1 kcal/mol, respectively, for 4FS and PFS deposition between 425 and 550 K. Films are shown by gel permeation chromatography to consist of low molecular weight polymer and oligimer species (between 3 and similar to 140 repeat units). Atomic farce microscopy analysis of films grown by this method indicates that the root mean square thickness variation along the surface is about 2.5%. [S0734-211X(99)01401-8].