Microscopic factors governing solute partitioning in ternary two-phase Al-Sc-Mg alloys are investigated combining three-dimensional-atom-probe (3DAP) microscopy measurements with first-principles computations. 3DAP is employed to measure composition profiles with subnanometer-scale resolution, leading to the identification of a large enhancement of Mg solute at the coherent alpha-Al/Al(3)Sc (fcc/L1(2)) heterophase interface. First-principles calculations establish an equilibrium driving force for this interfacial segregation reflecting the nature of the interatomic interactions.