This article focuses on the speciation of molten fluoride mixtures based on ThF 4 and UF 4 actinides used in molten salt reactors. The local structure of molten AF-MF 4 systems (A=Li + , Na + , K + ; M= Th 4+ , U 4+ ) was studied in situ by combining measurements by high temperature X-ray absorption spectroscopy and molecular dynamics simulations. In the molten state, 20°C higher than the melting temperature, these mixtures are composed of free fluorine and anionic species [MF 7 ] 3-, [MF 8 ] 4and [MF 9 ] 5whose distribution varies with the amount of MF 4 (M= Th 4+ , U 4+ ). Regardless of the cation, these complexes consist of an average of 8 Fneighbors for MF 4 content is less than 35 mol. %. This value decreases to 7 as the size of the alkaline ion A (A=Li + , Na + , K + ) increases. The [MF x ] 4-x species are linked together by bridging fluorine ions to form long chains [M x F Y ] 4x-y . The addition of a few percent UF 4 to the eutectic LiF-ThF 4 composition (77.5 mol% -22.5 mol. %) at 700°C leads to a slight increase in the population of free fluorine ions due to the breakdown of the Th-F links to form complexes [UF x ] 4-x isolated or connected to the (Th x F y ) 4x-y chains. This change in the structure of the liquid results in a slight decrease in viscosity when a few mol. % of UF 4 is added.