An optimized homogenization process for Al alloy ingots is key to subsequent material manufacturing, as it largely reduces metallurgical defects, such as segregation and secondary phases. However, studies on their exact microstructural evolution at different homogenization temperatures are scarce, especially for complex systems, such as the 2195 Al-Cu-Li alloy. The present work aims to elucidate the microstructural evolution of the 2195 Al-Cu-Li alloy during homogenization, including the dissolution and precipitation behavior of the TB (Al7Cu4Li) phase and S (Al2CuMg) phase at different homogenization temperatures. The results show that there are Cu segregation zones (Cu-SZ) at the dendrite boundaries with θ (Al2Cu) and S eutectic phases. When the temperature rises from 300 °C to 400 °C, fine TB phases precipitate at the Cu-SZ, and the Mg and Ag in the S phases gradually diffuse into the matrix. Upon further increasing the temperature to 450 °C, TB and θ phases at the grain boundaries are coarsened, and an S-θ phase transition is observed. Finally, at 500 °C, all TB and S phases are dissolved, leaving only θ phases at triangular grain boundaries. This work provides guidance for optimizing the homogenization procedure in 2195 alloys.