Abstract: Pyrometallurgical process is one of the most promising options for the advanced nuclear fuels cycle. Up to now, the molten salt electrorefining process, which was developed by Argonne National Laboratory(ANL), is the most practical pyrometallurgical process. However, the complete separation of actinides(An) from lanthanides(Ln) is still a challenge for the typical electrorefining process. The current investigations show that the deposition potential gaps of actinides and lanthanides on the solid Al cathode are bigger than those on other active cathodes, and therefore the separation of actinides from lanthanides by forming Al-An alloys are more promising for the partitioning and transmutation. This review is focused on the research progress concerning the separation of An from Ln by forming An-Al alloys for the pyrometallurgical process, and is involved in the following main parts: electrochemical behaviour of Ln on the formation of Ln-Al alloys; electrochemical behaviour of An on the formation of An-Al alloys; and the separation of An from Ln by forming An-Al alloys.