A new member to the A(2)IB(II)C(IV)X(4) compound family, Cu2ZnSbS4, was synthesized successfully using ball milling and postannealing in H2S-atmosphere. For comparative purposes, Cu3SbS4 was additionally prepared r using the same synthetic approach. As is common for A(2)IB(II)C(IV)X(4) compounds, Cu2ZnSbS4 crystallizes isostructural to Cu3SbS4 in the stannite-type structure in space group 142m. Both antimony sulfides contain monovalent diamagnetic copper and are characterized by substantial covalent bonding. This is consistent with the 121 Sb isomer shifts occurring for the Mossbauer spectra of Cu2ZnSbS4 (-7.71 mm s(-1)) and Cu3SbS4 (-7.68 mm s(-1)) which fall in the region of covalently bonded Sb (V) compounds. These spectroscopic results are supported by electronic structure calculations.