The electrochemical dissolution and passivation of laser additive manufactured Ti6Al4V were investigated through Tafel polarization, potentiostatic polarization and AC impedance measurements. The results show that the solution treatment-aging (STA) process aggravates the element micro-segregation compared to the annealing process, leading to varied Al and V contents of the phases from different samples. It is proven that either Al-rich or V-rich condition can highly affect the electrochemical dissolution behaviors due to thermodynamical instability caused by element segregation. The dissolution rate in the metastable passivation process is controlled by the stability of the produced film that is affected by phases distribution, especially the difficult-to-dissolve phase. And then, the dissolution rate of the phases in the transpassivation region is consistent with the rank in the activation process because the dense film is not capable of being produced. Compared to the annealed sample, the higher dissolution rate of the STA sample is beneficial to the electrochemical machining (ECM) of Ti6Al4V.