Electrochemical machining is a promising method for titanium alloy processing. The polarization characteristics of Ti6Al4V were studied in detail in order to provide a deeper understanding of this method. The polarization curve of the alloy, which shows the relationship between current density and potential under an external electric field, was obtained in NaBr electrolyte at three different concentrations in a three-electrode electrochemical test system. The surface topography of the polarization zone and pits was examined by scanning electron microscopy, and their fractal features were calculated by the picture point cover method. The results show that Ti6Al4V in the more concentrated electrolyte has higher dissolution rate, lower decomposition potential, and more uniform surface topology in the polarization areas.