The purpose of this study was to develop an accurate and precise analytical procedure for the determination of the content of antimony in coordination compounds of metal(II) hexafluoroantimonates(V) (M(SbF 6 ) 2 compounds, where M=Mg, Ca, Sr or Ba) synthesized in our laboratory. The major problem was to find an appropriate reagent for reductive decomposition of SbF 6 - to Sb 3 + required for the determination of antimony by redox titration. Effective reduction of Sb 5 + regardless of the metal M bound to SbF 6 - species was achieved using metallic aluminium powder in acidic medium. Precipitated Sb 0 was quantitatively reoxidized to Sb 3 + and determined potentiometrically with KBrO 3 or KMnO 4 . Other metals were determined complexometrically with disodium ethylenediaminetetraacetic acid (EDTA). Highly accurate and reproducible results were obtained in the concentration range 5-25 mg Sb with an RSD smaller than 0.6%. Antimony-fluoro-hydroxo species and fluoride did not interfere with the complexometric determinations of other metals with EDTA. The developed method enabled, for the first time, complete elemental chemical analysis of M(SbF 6 ) 2 compounds in the bulk form.