This work concerns the method of co-reduction process with aluminium ions in LiF–CaF2 medium (79–21 mol.%) on tungsten electrode for cerium and samarium extraction. Electrochemical techniques such as cyclic and square wave voltammetries, and potentiostatic electrolyses were used to study the co-reduction of CeF3 and SmF3 with AlF3. For each of these elements, specific peaks of Al–Ce and Al–Sm alloys formationwere observed by voltammetry aswell as peaks of pure cerium and aluminium, and pure samarium and aluminium respectively. The difference of potential measured between the solvent reduction and the alloy formation suggests expecting an extraction efficiency of 99.99% of each lanthanide by the process. Different intermetallic compounds were obtained for different potentiostatic electrolysis and were characterised by Scanning Electron Microscopy with EDS probe. The validity of the process was verified by carrying out cerium and samarium extractions in the form of Al–Ln alloy; the extraction efficiency was 99.5% for Ce(III) and 99.4% for Sm(III).