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The liquidus univariant lines of the Fe-Nb-B ternary system have been thermodynamically calculated by means of CALPHAD method and Fe-based thermodynamic data. It is found that there are two eutectic reactions in the Fe-rich comer, that is, (1) L(Fe-3Nb-15B) →α+ γ + M2B (1430 K), and (2) L(Fe-10Nb-27B) → FeB + Lc14+ M2B (1575 K).Moreover, the eutectic points are very close to the compositions with high glass forming ability determined experimentally.This means that it is feasible to design the compositions of multicomponent bulk metallic glasses by looking for the eutectic points in the Fe-Nb-B system by means of thermodynamic calculation.