The surface microstructure is one of the important factors to determine functions and properties of materials. It is necessary to characterize the surface microstructure for the purpose of controlling and designing. This review deals with mobilities and structures of functional groups adsorbed on the surfaces of inorganic solids after chemical modification. I focus on the measurements and simulations on the microstructures of normal saturated alkyl chains, since these chains have few complicated interaction between inter- and/or inter-molecules, such as hydrogen bonding.