Silicon substrates with hydrophobic coatings were prepared by self-assembled perfluoroalkylsilane films. Assembling time has a great effect on the surface properties of self-assembled films. Annealing process facilitated the migration of fluoroalkyl groups to the outmost surface. Triazole group is somewhat helpful to the regular arrangement of fluoroalkyl chains. Two fluoroalkyl groups packing densely in one molecule resulted in lower surface free energy.