In this study, the effect of Sc content on the microstructural characteristics and phase evolution of an Al–Cu–Li alloy under as-cast and homogenization conditions was investigated. The results show the grain refinement effect was distinct when the content of Sc was 0.16 wt%. However, further increased in Sc content resulted in a limited decrease in grain size. Besides, In the 0.16Sc alloy, the flocculent phase with primary Al3(Sc,Zr) phase coexisting with W (Al8-xCu4+xSc) phase appeared, and in the 0.32Sc alloy, the additional blocky primary Al3(Sc,Zr) phase was observed. With the increased of Sc content, the proportion of primary Al3(Sc,Zr) and W phases gradually increased, and the number and size of Al2Cu and Ag-containing Al2CuMg phases at grain boundaries gradually decreased. Two different morphologies of the primary W phase, flocculent and long strip shaped, were revealed within the Sc-containing alloy. The formation of the core-shell structure formed by Al3(Sc,Zr) particles and W phase was generated by the peritectic-eutectic reaction (Liquid + Al3(Sc,Zr)→α-Al + W) and the long strip of W phase was generated by the eutectic reaction (Liquid→α-Al + Al2Cu + W). During the homogenization process, the Al2Cu and Ag-containing Al2CuMg phases were completely re-dissolved after the two previous stages of homogenization, and only a small amount of the spheroidal residual W phase persisted. A subsequent low temperature treatment was employed to allow the Sc atoms that had diffused into the Al matrix to precipitate as Al3(Sc,Zr) dispersoids, resulting in a higher number density of Al3(Sc,Zr) particles for more efficiently utilizing the Sc elements.