Plasma treatment of polyimide surfaces not only causes structural modification during the plasma exposure, but also leaves active sites on the surfaces that are subject to post-reaction. In this work, the effects of atmospheric fluorine plasma treatment on the surface properties and dielectric properties of polyimide thin film were investigated by using X-ray photoelectron spectroscopy (XPS), Fourier transform-IR (FT-IR) spectroscopy, and contact angle measurement. The results indicated that plasma treatment successfully introduced fluorine functional groups on the polyimide surfaces. The polyimides also exhibited good thermal stability and a lower dielectric constant. It appears that the replacement of fluorine led to the decrease of the local electronic polarizability of polyimide. Consequently, it was found that the atmospheric fluorine plasma-treated polyimides possessed lower dielectric characteristics than the untreated polyimides.