Nyholmite, Cd3Zn2(AsO3OH)2(AsO4)2·4H2O, from the Block 14 Opencut, Broken Hill, New South Wales, Australia, is a new Cd-Zn arsenate species, isostructural with the minerals of the hureaulite group. The mineral occurs in a quartz-garnet-arsenopyrite matrix as white globules, tufted aggregates of fibrous crystals and radiating hemispheres of thin, colourless, bladed crystals. Associated minerals are goldquarryite, lavendulan-sampleite, scorodite-strengite and gypsum. Individual crystals are up to 0.2 mm in length and 0.05 mm across. The mineral is transparent to translucent with a vitreous lustre. It is brittle with an uneven fracture and a white streak. The Mohs hardness is 3–3.5 and the calculated density is 4.23 g cm–3 for the empirical formula. Electron microprobe analyses yielded CdO 34.58, ZnO 9.72, MnO 3.59, CuO 3.39, Al2O3 0.20, CaO 0.16, PbO 0.37, As2O5 34.55, P2O5 6.29 totalling 92.85 wt.%. The empirical formula, based on 20 oxygen atoms, is Ca0.03Pb0.02 Cd2.80Al0.04Zn1.24-Cu0.44Mn0.53[(AsO4)3.13(PO4)0.92]Σ4.05H1.91·3.79H2O. Nyholmite is monoclinic, C2/c, a = 18.062(4) Å, b = 9.341(2) Å, c = 9.844(2) Å, β = 96.17(3)°, V = 1651.2(6) Å3 (single-crystal data, at 123 K). The six strongest lines in the X-ray powder diffraction pattern are [d(Å),I,(hkl)]: 8.985,30,(200); 8.283,85,(110); 6.169,25,(111); 4.878,25,(002); 3.234,100,(2, 420); 3.079,65,(222, 511); 2.976’45’(113). The crystal structure was solved by Patterson methods and refined using 2045 observed reflections to R1(F) = 3.73%. The structure is characterized by a kinked, five-membered chain of edge-sharing Mφ6 (φ = unspecified anion) octahedra, or pentamer, that extends in the a direction. The pentamers link by sharing corners to form a sheet in the (001) plane. Pentamers are also linked, via corner-sharing, by (As,P)O4 groups forming thick slabs in the (001) plane. The slabs link in the c direction by cornersharing between octahedra and tetrahedra to form a dense heteropolyhedral framework. Moderate to weak hydrogen-bonding provides additional linkage between the slabs.