It is well known that the microstructure distribution in recycled Al-Si alloys has a large impact on the final mechanical properties. In this study, the microstructure, including Fe-rich intermetallics and microporosity, was quantitatively adjusted using multi-scale characterization with microalloying rare earth elements and traditional grain refiners as the objects of study. It was found that the addition of Al-Ti-B to W319 recycled aluminum alloy reduces the microstructure size and Fe-rich intermetallics, while the addition of La facilitates the transformation of harmful β-Fe into less harmful particles and the densification of coarse eutectic Si, promoting the refining effects on the microstructure additionally. Therefore, the RE and Al-Ti-B master alloy could be a potential new grain refining agent, especially for Al-cast alloys when the ductility is critical for designing. The improvement in elongation far exceeds the original level, up to 69.6%, while maintaining the same level of strength or even better. At the same time, the excessive addition of La may lead to the depletion of Cu and Ti elements during heat treatment, degrading ductility and strength.