Performance of future generations of integrated circuits will be limited by the RC delay caused by on-chip interconnections. Overcoming this limitation requires the deployment of new high conductivity metals such as copper and low dielectric constant intermetal dielectrics (IMD). Fluorinated amorphous carbon (a-CFx) is a promising candidate for replacing SiO2 as the IMD. In this paper we investigated the structure and electronic properties of a-CFx thin films using high-resolution x-ray absorption, emission, and photoelectron spectroscopy. The composition and local bonding information were obtained and correlated with deposition conditions. The data suggest that the structure of the a-CFx is mostly of carbon rings and CF2 chains cross-linked with C atoms. The effects of growth temperature on the structure and the thermal stability of the film are discussed.