The structure and constitution of plasma-polymerized film of C3F6 (PPHFP) have been investigated by measuring its ESCA, 19F-NMR, and IR spectra. It is found that the PPHFP film was a high degree of branching and 57% of quaternary carbons are linked to CF3 groups. It is also found that the constitution of PPHFP film is changed greatly at high power and a large amount of Si and O atoms are linked to the PPHFP chains. Furthermore, using element analysis, ESCA, and theoretical calculation by electronegative model, we found that the nitrogen atoms get into the PPHFP chains when using N2 as plasma gas. Besides, the radical concentration in the film is obtained to be 9.97 × 1019 spins/g and its half-life is about half a year at room temperature in Ar gas. Having investigated decay process of the radicals in two gases of air and Ar, we calculated the activation energies and rate constants of radical recombination and oxidation reactions at different temperatures.