Graphene oxide (GO) has been recognized as an amphiphilic molecule or a soft colloidal particle with the ability to adsorb and assemble at the liquid/liquid (L/L) interface. However, most extant works concerning the adsorption behaviors of GO at the L/L interface have been limited to the non-polarized L/L interface. Here, we studied what would happen if GO nanosheets met with a polarizable L/L interface, namely an interface between two immiscible electrolyte solutions (ITIES). On one hand, the adsorption behavior of GO nanosheets at the L/L interface was electrochemically investigated firstly by using cyclic voltammetry (CV) and alternating current voltammetry (ACV). On the other hand, the influence of the adsorbed GO layers at the L/L interface on the ion transfer reactions was studied by employing ion-transfer voltammetry of TEA + and ClO 4 - selected as probe ions. Capacitance measurements show that the interfacial capacitance increases greatly in the presence of GO nanosheets inside the aqueous phase, which can be attributed to the increases of interfacial corrugation and charge density induced by the parallel adsorption and assembly of GO at the L/L interface. In addition, it is found that the application of an interfacial potential difference by external polarization can promote the adsorption of GO at the L/L interface. Moreover, the ion-transfer voltammetric results further demonstrate that the GO layers formed at the interface can suppress the ion transfer reactions due to interfacial blocking and charge screening, as well as the hindrance effect induced by the GO layers. All the results with insights into the interfacial behavior of GO under polarization with an external electric field enable understanding the adsorption behavior of GO at the L/L interface more comprehensively.