Two new silver-antimony sulfides, [C2H9N 2][Ag2SbS3] (1) and [C2H 9N2]2[Ag5Sb3S 8] (2), have been prepared solvothermally in the presence of ethylenediamine and characterized by single-crystal X-ray diffraction, thermogravimetry, and elemental analysis. Compound 1 crystallizes in the space group Pn (a = 6.1781(1) Å, b = 11.9491(3) Å, c = 6.9239(2) Å, ß = 111.164(1)°) and 2 in the space group Pm (a = 6.2215(2) Å, b = 15.7707(7) Å, c = 11.6478(5) Å, ß = 92.645(2)°). The structure of 1 consists of chains of fused five-membered Ag2SbS 2 rings linked to form layers, between which the template molecules reside. Compound 2 contains honeycomb-like sheets of fused silver-antimony-sulfide six-membered rings linked to form double layers. The idealized structure can be considered to be an ordered defect derivative of that of lithium bismuthide, Li3Bi, and represents a new solid-state structure type.