Syngas is the product of gasification processes and is used for the production of petrochemicals. Little attention has been paid to its use in the production of oligomeric thin films under ambient conditions. Herein, the nature of the photoinitiated chemical vapor deposition of films made from syngas using high-wavelength ultraviolet light is discussed, including an exploration of the oligomeric films' structure, synthesis mechanism, and growth kinetics. Specifically, X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry analyses provide insight into the chemical structure, illustrating the effect of photogenerated radicals in the formation of aliphatic, anhydride, and cyclic structures. The films are covalently bonded to the substrate and chemically uniform. Electron and atomic force microscopy identify an islandlike morphology for the deposit. These insights into the mechanism and structure are linked to processing parameters through a study on the effect of residence time and treatment duration on the deposition rate, as determined through profilometry.