Lithium-ion is transferred through a variety of surfaces and interfaces in Lithium-ion batteries during the process of charging and discharging. The properties of surface and interface of electrode have great influence on the power density, energy density, the efficiency of charging and discharging, service life, cycling stability. In general, the structure of surface and interface of material are different from that of bulk, direct observation upon atomic-scale structure of electrode in different electrochemical state contributes to studying electrochemical reaction mechanism and evolution of properties and is of instructive significance to improve the properties of Lithium-ion batteries. In this paper , we review the recent progress in investigations of surface and interface structure of electrode materials, introduce special interface, SEI, the phase transition of surface and doping of surface, discuss the inherent correlation between the atomic-scale structures of surface and interface of electrode materials and their performance, raise some advises to improve the performance of Lithium-ion batteries and look forward to the development of Lithium-ion batteries in the aspect of increasing of energy density ,averting side reaction of solid electrode and liquid electrolyte and properties improvement.