To analyze the effect of lithium and microstructure on the pitting corrosion behavior of aluminum alloys, three types of aluminum alloys were studied via scanning electron microscopy, transmission electron microscopy, electrochemical polarization, and by immersion tests coupled with in-situ observation of pitting and statistical analysis of pit depths measured by surface profilometry. It was found that, with increasing lithium content, the resistance to pitting corrosion was enhanced and the passive range was enlarged. In-situ observation revealed that the development of pitting corrosion exhibited three stages, including an initial slow nucleation stage (Stage I), a fast development stage (Stage II), and a stabilized growth stage (Stage III). Higher lithium content contributed to shorter time periods of Stages I and II, resulting in faster pitting evolution and a higher number of pits. However, the pits were generally shallower for the specimen with the highest lithium content, which is in agreement with the results of the electrochemical analysis.