Surface and interface play critical roles in energy storage devices, calling for operando characterization techniques to probe the electrified surfaces/interfaces. In this work, surface science methodology, including electron spectroscopy and scanning probe microscopy, has been successfully applied to visualize electrochemical processes at operating electrode surfaces in an Al/graphite model battery. Intercalation of anions together with cations is directly observed in the surface region of a graphite electrode with tens of nanometers thickness, the concentration of which is one order higher than that in bulk. An intercalation pseudocapacitance mechanism and a double specific capacity in the electrode surface region are expected based on the super-dense intercalants and anion/cation co-intercalation, which are in sharp contrast to the battery-like mechanism in the electrode bulk. The distinct electrochemical mechanism at the electrode surface is verified by performance tests of real battery devices, showing that a surface-dominant, nanometer-thick graphite cathode outperforms a bulk-dominant, micrometer-thick graphite cathode. Our findings highlight the important surface effect of working electrodes in charge storage systems.