Trifluoromethane (CHF3) was used as a precursor gas in pulsed-plasma enhanced CVD to deposit fluorocarbon films onto Si substrates. The film composition, as measured by X-ray photoelectron spectroscopy (XPS) of the C1s peak, was observed to change as the plasma duty cycle was changed by varying the plasma off-time; this offers a route to control the molecular architecture of deposited films. FTIR results indicate that the film is primarily composed of C-x, components, with little or no C-H incorporation into the film. The rms roughness of the films is extremely low, approaching that of the Si substrate; the low growth rate and consequent high-power input/thickness is believed to be partly responsible. CHF3 produces films with higher % CF2 compared to other hydrofluorocompound (HFC) monomers (CH2F2 and C2H2F4). However, the deposition kinetics for all three HFC gases display similar trends. In particular, at a fixed on-time of 10 ms, the deposition rate per pulse cycle reaches a maximum at an off-time of approximately 100 ms.