Two series of perfluorinated carboxylic acid (FC) and hydrogenated carboxylic acid (HC) self-assembledmonolayer (SAM) films were prepared on aluminum surfaces separately by chemical vapor deposition. The formation, structure and morphology of these films were characterized by measuring contact angle with ellipsometric method, x-ray photoelectron spectrometry, and atomic force microscopy, respectively. FC and HC SAMs with long chains formed more densely packed films than those with short chains did. The comparative micro/nanoscale friction and adhesive properties of FC and HC SAMs, with various chain lengths on aluminum-coated silicon substrate, were investigated. The influence of environmental conditions, such as relative humidity (RH) and temperature, on the friction and adhesion behavior was studied. Micro/nanotribological properties of the films were greatly influenced by their backbones and terminal groups. FC SAMs with long chain exhibited adhesion-resistance, friction reduction, and environmental independence