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The isothermal sections of the phase diagram of the V–Fe–Sb ternary system have been constructed at 870 and 1070 K by means of X‐ray and electron‐probe microanalyzer (EPMA) analyses over the whole concentration range. The existence of the one ternary phase, VFeSb, with MgAgAs‐ and Ni2In‐type structures was observed at 870 and 1070 K, respectively. The solid solution formed based on the binary Fe2–xSb (Ni2In‐type) compound reaches up to 12 at.‐% of V at 870 K and 40 at.‐% at 1070 K, respectively. Differential scanning calorimetry (DSC) analysis, magnetic susceptibility measurements, and electronic structure calculations showed the absence of a VFeSb polymorph phase transition and indicate that the hexagonal phase is part of the VyFe2–xSb solid solution.