Titanium alloys exhibits high corrosion resistance owing to the spontaneous formation of protective oxide film when exposed to oxygen environment. Ti6Al4V is an (α+β) titanium alloy and its dissolution depends on the microstructure i.e., distribution of α and β phases and the formation of the oxide layer. In this work, the electrochemical characteristics of Ti6Al4V alloy under different heat treatment conditions were investigated using 1M NaBr solution as an electrolyte. It was found that with the heat treatment condition of 1050FC (i.e. heat treatment temperature above β transus temperature and furnace cooling), a less passive oxide film is formed as compared to the other heat treatment conditions. The electrochemical dissolution behaviour is further verified by electrochemical micromachining (ECMM) of the alloy via fabricating micro-dimples. It was concluded from electrochemical dissolution study and ECMM that the 1050FC alloy dissolves quickly compared to the other heat treated alloys.