A study of the effect of lithium content (1, 3 and 5wt.%) and heat treatment (400°C during 144h) on the corrosion behavior of Ni3Al alloy has been carried out in a 62mol.%Li2CO3–38mol.%K2CO3 mixture at 650°C using electrochemical techniques. Employed electrochemical techniques included potentiodynamic polarization curves, linear polarization resistance, LPR, electrochemical impedance spectroscopy, EIS, and electrochemical noise, measurements EN. Results have shown that the alloys exhibited an active–passive behavior regardless of the heat treatment. For alloys without heat treatment, the most corrosion resistant was the Ni3Al base alloy, but when they were heat treated, the most corrosion resistant was the alloy containing 3%Li. EIS results showed that for short immersion tests, the corrosion process was under diffusion control, but for longer exposure times, the presence of a protective scale was evident. All the alloys were highly susceptible to a localized type of corrosion according to EN measurements and supported by SEM micrographs.