Electron transport is a fundamental process that controls the intrinsic chemical and physical properties of solid materials. The surface phase becomes dominant when downsized dimensionality into cluster scale in nanomaterials, and surface chemistry plays more and more important role in regulating electron transport. During past decades, varieties of chemical approaches have been developed to modify the surface of low dimensional solids, substantially providing versatile perspectives on engineering electron transport. In this Perspective, we focus on recent researches concerning surface chemical modification strategies, such as surface molecular adsorption, atomic incorporation, defect engineering and spin scattering to engineer electron transport of typical one-/two-dimensional systems. Under the framework of Drudes transport model, we highlight the core role of micro degrees of freedom, i.e., charge, lattice, and spin, in molecular-level understanding and optimizing the regulation effect of surface chemistry. Finally, based on the discussion and current achievements of surface chemistry effect on electron transport of low dimensional solids, some personal perspectives on the future development are also presented.