AbstractThe chemistry and the crystal structure of the recently described mineral argentopolybasite are critically discussed based on the study of two new occurrences of the mineral: Gowganda, Timiskaming District, Ontario, Canada and IXL Mine, Silver Mountain mining district, Alpine County, California.The crystal structure of argentopolybasite can be described as the sequence, along the c axis, of two alternating layers: a [Ag₆Sb₂S₇]^2–A layer and a [Ag₁₀S₄]²⁺B layer. In the B layer there are linearly-coordinated metal positions (B sites), which are usually occupied by copper in all members of the pearceite–polybasite group, resulting in a B-layer composition [Ag₉CuS₄]²⁺. In argentopolybasite, however, Ag fills all the metal sites in both A and B layers. By means of a multi-regression analysis on 67 samples of the pearceite–polybasite group, which were studied by electron microprobe and single-crystal X-ray diffraction, the effect of Ag, Sb and Se on the B sites of the B layer was modelled. Although the nomenclature rules for these minerals are based on chemical data only, we think this approach is useful to evaluate the goodness of the refinement of the structure (Ag/Cu disorder) and thus fundamental to discriminate different members of the pearceite–polybasite group.