A study has been made of insertion of lithium into silver hafnium sulfides by soft chemical method using n-butyl lithium. As the starting ternary compounds, orthorhombic Ag2HfS3 (S.G Cmca with a = 11.458 Angstrom, b = 6.628 Angstrom and c = 12.774 Angstrom) and cubic Ag4Hf3S8 (S.G P4(3)32 with a = 10.9015 Angstrom) synthesized from solid state reaction were chosen. Lithiated products were examined with an X-ray powder diffraction, chemical analyses and conductivity measurements. In both cases polycrystalline new phases were derived together with the occurrence of native silver. Within them only the lithiated Ag4Hf3S8 phase could be indexed by a cubic cell with a = 10.4327(9) Angstrom. Its chemical composition has been determined to be Li5Ag2Hf3S8 by ICP-AES method. Structure model is discussed on the basis of topochemical replacement reaction. The OCV of Li/Li+/sample measured are 2.5 V for Ag4Hf3S8 and 2.1 V for Li5Ag2Hf3S8 respectively.