The thermal stability of perfluoralkylsiloxane monolayers in a vacuum is investigated via X-ray photoelectron spectroscopy (XPS) for temperatures up to 600 degrees. 1H, 1H,2H,2H,-perfluorodecyltrichlorosilane (FDTS) monolayers are deposited on oxidized Si(l 00) surfaces from the vapor phase with various degrees of surface coverage. Significant monolayer desorption is observed to occur at temperatures below 300 degrees C regardless of the initial monolayer coverage. The desorption mechanism follows first-order kinetics and is independent of the initial coverage. Removal of FDTS is found to occur by the loss of the entire molecular chain, as evidenced by the fact that the CF3/CF2 peak area ratios remain unaffected by the annealing process although CFn/Si peak ratio declines with annealing. This is in sharp contrast to the behavior observed for octadecyltrichlorosilane monolayer for which elevated temperature leads to C-C bond breakage and successive shortening of the alkyl chain. It is also shown that the binding energy and the shape of the F 1s line are good indicators of the degree of disorder in the chain, as well as a measure of the interaction of the chain with the silicon surface.