TiNi alloys have excellent shape memory properties and corrosion resistance as well as high biocompatibility. This study investigated the effects of copper addition on the phase transitions and electrochemical corrosion behaviors of Ti50Ni50-xCux alloys. TiNi, Ti50Ni47Cu3, Ti50Ni44Cu6, and Ti50Ni41Cu9 alloys were prepared using vacuum arc remelting followed by 4 h homogenization at 950°C. Differential scanning calorimetry and X-ray diffraction analyses were conducted. The corrosion behaviors of the alloys were evaluated using potentiodynamic polarization test in Hank’s balanced salt solution at a temperature of 36.5 ± 1°C. The TiNi alloy showed phase transitions from the cubic B2 phase to the monoclinic B19’ phase when the alloy was thermally cycled. The addition of copper to the TiNi alloy played a major role in stabilizing the orthorhombic B19 phases during the phase transitions of Ti50Ni50-xCux alloys. The shifts in the corrosion potential toward the positive zone and the low corrosion current density were affected by the amount of Cu added. The corrosion resistance of the TiNi alloy increased with increasing copper content.