Abstract Nuffieldite, a rare bismuth sulfosalt from Alice Arm, British Columbia, is orthorhombic, space group Pbnm, with a = 14.387(7), b = 21.011(15), c = 4.046(6) Å, ϱ meas = 7.01(7) g cm−3 and ϱ cal = 7.21 g cm−3 for Z = 4. Intensity data were photographically recorded with an integrating equi-inclination Weissenberg camera employing the multiple-film technique, and were measured with the aid of an automated photoscanner. The structure was solved with the symbolic addition procedure and refined, by least-squares techniques, to a disagreement index of 14.1%. The asymmetric unit of the structure contains 13 atoms: 5 heavy-metal atoms, Cu, and seven S atoms. On the basis of interatomic distances and coordination geometry, Pb and Bi were each assigned to a pair of heavy-metal sites; a fifth site is believed to contain Pb and Bi in disorder. The Cu atom is in tetrahedral coordination. The dominant feature of the structure is a quadruple PbBiS3 chain which is flanked by a pair of chains with Cu in tetrahedral coordination. This structural unit is identical to that found in the simpler sulfosalt aikinite, PbCuBiS3. The aikinite-like ribbons share an edge with a pair of new three-membered chains to form ten-membered ribbons which are linked only by Cu tetrahedra and weak secondary bonds.