The microstructure evolution and composition distribution of as-cast and homogenized 2099 aluminumlithium (Al-Li) alloy were studied by optical microscopy (OM), differential thermal analysis (DTA), scanning electron microscopy (SEM), energy dispersive spectrometry (EDS), area and line scanning, X-ray diffraction (XRD), and Vickers microhardness test methods. The results show that severe dendrite exists in the as-cast alloy. Cu, Zn, Mn, and Mg distribute unevenly from the grain boundary to inside. The low-melting point nonequilibrium eutectic phases dissolve into the matrix during the first-step homogenization, whereas the melting point of residual eutectic phases is elevated. After the second-step homogenization, most of the remaining eutectic phases dissolve into the matrix, except a small amount of Al-Cu-Fe phases. An optimized homogenization process of the 2099 Al-Li alloy is developed (515°C 9 18 h ? 525°C 9 16 h), which shows a good agreement with the homogenization kinetic analysis results.