It is still controversial where the improved stability of n-octadecyltriethoxysilane self-assembled monolayer (OTE SAM) on plasma-pretreated mica surface exactly originates from. To date, it has been well known that the extensive cross-polymerization between silane headgroups is a crucial factor for the outstanding mechanical strength of the monolayer. However, this study directly observed that the stability comes not only from the cross-links but also, far more importantly, from the direct chemical bonds between silane headgroups and mica surface. To observe this phenomenon, n-octadecyltrichlorosilane monolayers were self-assembled on both untreated and plasma treated mica surfaces, and their adhesion properties at various stress conditions and force profiles in pure water were investigated and compared through the use of the surface forces apparatus technique. It revealed that, in pure water, there is a substantial difference of stability between untreated and plasma treated cases and the plasma treated surface is mechanically much more stable. In particular, the protrusion behavior of the monolayer during contact repetition experiment was always observed in the untreated case, but never in the plasma treated case. It directly demonstrates that the extensive chemical bonds indeed exist between silane head-groups and plasma treated mica surface and dramatically improve the mechanical stability of the OTE monolayer-coated mica substrate.