Abstract Photonic thin films have been grown on a variety of substrates using plasma-enhanced chemical vapor deposition (PECVD) of organic monomers, namely benzene and octafluorocyclobutane (OFCB). Films produced by both homo-polymerization and co-polymerization have been prepared and analyzed. In order to introduce significant contributions from OFCB into co-polymerized films, the OFCB was introduced directly into the plasma zone and the benzene flow was reduced to a low, stable level using a high-accuracy metering valve. The films have been characterized by X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) and variable-angle spectroscopic ellipsometry (VASE), with an emphasis on XPS. Apart from determining the atomic composition of the films with XPS, it was extremely valuable in determining the chemistry of the films. Studies of the mechanisms of the homo- and co-polymerization reactions have aided in the fabrication of photonic films.