In this paper, a novel method to fabricate nano-metal electrodes and scanning electrochemical microscopy (SECM) tips has been developed, and fabricated electrodes were characterized by scanning electron microscopy (SEM), cyclic voltammetry and SECM. Based on the combination of nanoelectrodes (including metal and glass pipets) and SECM, and the droplet three-electrode system developed previously by our group, we have investigated the charge (electron and ion) transfer kinetics at the polarizable liquid/liquid interfaces. The experimental results demonstrate that the facilitated ion transfer (FIT) at liquid/liquid interface is potential dependent in a certain region, and the electron transfer (ET) kinetics can be explained by using the Marcus theory when the concentrations of the redox couple for each phase are appropriate.