The interface structure in copolymer films made using plasma enhanced chemical vapor deposition (PECVD) has been probed for the first time using X-ray reflectivity. Copolymer films made from comonomers benzene (B), octafluorocyclobutane (OFCB), and hexamethyldisiloxane (HMDS) show extremely sharp interfaces and scattering length density depth profiles that are uniform with depth, making them useful for optical applications. The polymer/air interface has an rms roughness (∼5 Å) that is only slightly larger than that of the supporting substrate (∼3 Å). Addition of either benzene or HMDS as a comonomer in the deposition of OFCB alters a transient deposition behavior at the silicon oxide interface that occurs when using only OFCB. For the B–OFCB copolymer films, a facile control of refractive index with monomer feed composition is achieved. A nonlinear variation in the X-ray scattering length density with composition for the HMDS–OFCB copolymer films is consistent with the nonlinear visible light refractive index (632.8 nm) variation reported earlier.