The increasing use of small micromechanical devices and advanced sensors has led to concern about the failure modes and reliability of these structures. The enormous promise will not materialize without substantial progress in overcoming the stiction, friction and wear associated with such devices and understanding the mechanical behavior of MEMS materials and structures. Self-assembled monolayers (SAMs) are release and anti-stiction coatings for MEMS. In this paper, the anti-stiction properties of octadecyltrichlorosilane (OTS) SAM were calculated. The microtribological properties of OTS SAM were investigated with a ball-on-flat microtribometer. The influence of OTS SAM on the mechanical properties of micromachined polysilicon films for MEMS was investigated with an accurate evaluation using the microtensile test device. It was concluded that the OTS SAM has good anti-stiction properties and low friction coefficients. The hydrophobic property of OTS is the main factor leading to an increase in the average fracture strength of micromachined polysilicon up to 32.46%. Thus, the operational stability and lifetime of MEMS can be raised when coated with self-assembled monolayers.