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Due to the interesting properties of the Sb₃Zn₄ thermoelectric material, and its potential use as substitute of PbTe, a reliable preparation method of this alloy is required. As contradictions exist not only in the experimental data reported in the literature as well as in the two existent thermodynamic description for the equilibrium phases of the system Sb-Zn, a new investigation on this system was done. As results the existence of Sb₅Zn₆ is not confirmed, the range of homogeneity of the phase Sb₃Zn₄ is quantitatively determined (56.5-57 at.%Zn), a high temperature transformation of this phase is proposed. An easy method to prepare Sb₃Zn₄ from the melt is reported. Further work on characterization of the crystal structure of the high temperature phase as well as a new thermodynamic reassessment is being performed.