Charge (ion and electron)-transfer reactions at a liquid/liquid interface are critical processes in many important biological and chemical systems. An ion-transfer (IT) process is usually very fast, making it difficult to accurately measure its kinetic parameters. Nano-liquid/liquid interfaces supported at nanopipettes are advantageous approaches to study the kinetics of such ultrafast IT processes due to their high mass transport rate. However, correct measurements of IT kinetic parameters at nanointerfaces supported at nanopipettes are inhibited by a lack of knowledge of the nanometer-sized interface geometry, influence of the electric double layer, wall charge polarity, etc. Herein, we propose a new electrochemical characterization equation for nanopipettes and make a suggestion on the shape of a nano-water/1,2-dichloroethane (nano-W/DCE) interface based on the characterization and calculation results. A theoretical model based on the Poisson-Nernst-Planck equation was applied to systematically study how the electric double layer influences the IT process of cations (TMA+, TEA+, TPrA+, ACh+) and anions (ClO4-, SCN-, PF6-, BF4-) at the nano-W/DCE interface. The relationships between the wall charge conditions and distribution of concentration and potential inside the nanopipette revealed that the measured standard rate constant (k0) was enhanced when the polarity of the ionic species was opposite to the pipette wall charge and reduced when the same. This work lays the right foundation to obtain the kinetics at the nano-liquid/liquid interfaces.