The important role of surface chemistry was reviewed in order to understand microtribology. Tribological properties are closely dependent on surface chemical states at the friction interface. Organic films provide a good lubricity at the thickness more than monolayer. Conformation of molecules in the surface films affects tribological properties. The thin layer lubricants on magnetic recording disks are decomposed tribochemically even under a low load and the decomposition was strongly affected by the surface activity of the slider materials. The chemical nature of nascent surfaces and exoemission were discussed as an active source for the tribochemical reactions.