Abstract The influence of thermo-mechanical processing (TMP) on the microstructure and the electrochemical behavior of new metastable β alloy Ti-20.6Nb-13.6Zr-0.5V (TNZV) was investigated. The TMP included hot working in below β transus, solution heat treatments at the same temperature and different cooling rates in addition to aging. Depending upon the TMP conditions, a wide range of microstructures with varying spatial distributions and morphologies of equiaxed/elongated β and β phases were attained, allowing for a wide range of electrochemical properties to be achieved. The corrosion behavior of the studied alloy was evaluated in a Ringer's solution at 37 °C via open circuit potential-time and potentiodynamic polarization measurements. © 2015 The Nonferrous Metals Society of China.