Three framework silver-thiciantimonates, K3Ag9Sb4S12 (1), Rb3Ag9Sb4S12(2), and Cs3Ag9Sb4S12(3), and one layeied silver-thioarsenate, CsAg2AsS3(4), have been synthesized solvothermally in the presence of thiophenol as a mineralizer. Compounds 1, 2, and 3 are isostructural and contain infinite silver-sulfur chains [Ag9S12](15-). These chains are connected to one another by the antimony atoms to generate wide channels along the [001] direction where the elkali metal cations reside. The structure of 4 consists of helical chains [Ag2S3](4-) linked by the arsenic atoms to form layers with potassium ions between the layers.