Jet electrochemical micromilling (JEMM) exhibits significant potential for high-efficiency and high-quality machining of titanium alloy microstructures. However, during the JEMM process, the machined surface of the workpiece inevitably experiences stray current attacks at low current levels. Due to the formation of a dense passive film on the surface of the titanium alloy under electrochemical action, stray corrosion occurs on the machined surface. Hence, the electrochemical dissolution behavior of titanium alloys at low current densities directly impacts both machining efficiency and quality. This study first analyzed the effects of electrolyte composition and current density on the transpassive potential, breakdown of the passive film, current efficiency, and the dissolved surface on Ti-6Al-4V. The transpassive potential and electrochemical impedance of Ti-6Al-4V were found to be lower in NaCl solution than in NaNO3 solution. In addition, lower current densities enabled higher current efficiency and resulted in a more uniform and flat dissolution surface. Subsequent experiments used these two solutions for JEMM of complex-shaped microstructures on Ti-6Al-4V. The findings demonstrated that, compared to the NaNO3 solution, the use of NaCl solution increases the material removal rate by approximately 30%, enhances the aspect ratio by about 26%, and reduces surface roughness by roughly 58%. This indicates that employing NaCl solution can lead to superior machining efficiency and quality.