We have studied a series of homoleptic polyfluorinated mercury thiolates, [Hg(SRF)(2)] (R-F = C6F4(CF3)-4 1, C6F5 2, C6HF4-4 3, C6H4F-2 4, C6H4F-3 5, C6H4F-4 6, C6H4(CF3)-2 7, C6H4(CF3)-3 8, C6H4(CF3)-4 9, C6H4(OCF3)-4 10, C6H3F2-3,5 11 and C6H3(CF3)(2)-3,5 12) synthesized by methatetical reactions of the corresponding fluorinated thiols with mercury(II) acetate. The Hg-199 NMR chemical shift data for this series of homoleptic Hg(II) complexes spans over the range from ca. -1300 up to ca. -1400 ppm. Upfield chemical shifts in these NMR spectra are seen for perfluorinated ligands and there seems to be a correlation between the number of fluorine atoms on the aromatic ring (or group electronegativity), their relative positions on the ring and the corresponding chemical shifts. We also report the X-ray diffraction crystal structure of the complex [Hg(SC6H4(CF3)-2)2]7. The molecule crystallizes in the space group P-1 with an almost perfect linear coordination (S-Hg-S 177.03(5)) around the Hg(II) atom.