The titanium alloy Ti-6Al-4V is used in many industries including aviation, automobile manufacturing, and medical equipment, because of its low density, extraordinary corrosion resistance and high specific strength. Electrochemical machining (ECM) is a non-traditional machining method that allows applications to all kinds of metallic materials in regardless of their mechanical properties. It is widely applied to the machining of Ti-6Al-4V components, which usually takes place in a multicomponent electrolyte solution. In this study, a 10% NaNO3 solution was used to make multiple holes in Ti-6Al-4V sheets by through-mask electrochemical machining (TMECM). The polarization curve and current efficiency curve of this alloy were measured to understand the electrical properties of Ti-6Al-4V in a 10% NaNO3 solution. The measurements show that in a 10% NaNO3 solution, when the current density was above 6.56 A·cm-2, the current efficiency exceeded 100%. According to polarization curve and current efficiency curve, an orthogonal TMECM experiment was conducted on Ti-6Al-4V. The experimental results suggest that with appropriate process parameters, high-quality holes can be obtained in a 10% NaNO3 solution. Using the optimized process parameters, an array of micro-holes with an aperture of 2.52 mm to 2.57 mm and maximum roundness of 9 μm were produced using TMECM.