Structural characteristics of poly(tetrafluoroparaxylylene) (PA-F) films deposited directly from C6H4(CF2Br)2 precursor have been studied using Fourier transform infrared spectroscopy (FTIR) and x-ray photoelectron spectroscopy (XPS). Zn was used as the catalyst and the vapor pyrolysis of precursor was carried out between 350 and 400 °C. It is shown that the FTIR and XPS spectra of the PA-F films deposited from the precursor are comparable to those made from the conventional dimer route. Dissociation of the PA-F films does not occur up to an annealing temperature of 500 °C. Both Zn and Br contaminants were observed in the XPS spectra. However, we found that the Br contamination disappears after annealing to an elevated temperature (≥350 °C), while Zn impurities still remain in the film.