Micro/nano adhesion and friction properties of self-assembled monolayers (SAMs) with different head- and end-group were experimentally studied according to the coating methods. Various kinds of SAM having different spacer chains (C10 and C18), head-group and end-group were deposited onto Si-wafer by dipping and chemical vapour deposition (CVD) methods under atmospheric pressure, where the deposited SAM resulted in the hydrophobic nature. The adhesion and friction properties between tip and SAM surfaces under nano scale applied load were measured using an atomic force microscope (AFM) and also those under micro scale applied load were measured using a ball-on-flat type micro-tribotester. Surface roughness and water contact angles were measured with SPM (scanning probe microscope) and contact anglemeter respectively. Results showed that water contact angles of SAMs with the end-group of fluorine show higher relatively than those of hydrogen. SAMs with the end-group of fluorine show lower nano-adhesion but higher micro/nanofriction than those with hydrogen. Water contact angles of SAMs coated by CVD method show high values compared to those by dipping method. SAMs coated by CVD method show the increase of nano-adhesion but the decrease of nano-friction. Nano-adhesion and friction mechanism of SAMs with different end-group was proposed in a view of size of fluorocarbon molecule.