A new mineral, yaroshevskite, ideally Cu9O2(VO4)4Cl2, occurs in sublimates collected from the Yadovitaya fumarole at the Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka, Russia. It is associated with euchlorine, fedotovite, hematite, tenorite, lyonsite, melanothallite, atlasovite, kamchatkite and secondary avdoninite, belloite and chalcanthite. Yaroshevskite forms isolated prismatic crystals, up to 0.1 × 0.15 × 0.3 mm in size, on the surface of euchlorine crusts. The mineral is opaque and black, with a reddish black streak and lustre between metallic and adamantine. Yaroshevskite is brittle, no cleavage was observed and the fracture is uneven. The Mohs hardness is ~3½ (corresponding to a mean VHN micro-indentation hardness of 172 kg mm−2) and the calculated density is 4.26 g cm−3. In reflected light, yaroshevskite is grey with a weak bluish hue. Pleochroism, internal reflections and bireflectance were not observed. Anisotropy is very weak. The composition (wt.%) determined by electron microprobe is: CuO 61.82, ZnO 0.53, Fe2O3 0.04, V2O5 31.07, As2O5 0.32, MoO3 1.56, Cl 6.23, O=Cl2 −1.41; total 100.16. The empirical formula, calculated on the basis of 20 (O + Cl) anions is (Cu8.80Zn0.07Fe0.01)Σ8.88 (V3.87Mo0.12As0.03)Σ4.02O18.01Cl1.99. Yaroshevskite is triclinic, space group P1İ, a = 6.4344(11), b = 8.3232(13), c = 9.1726(16) Å, α = 105.338(14), β = 96.113(14), γ = 107.642(1)°, V = 442.05(13) Å3 and Z = 1. The nine strongest reflections in the X-ray powder pattern [dobs in Å(I)(hkl)] are as follows: 8.65(100)(001); 6.84(83)(01İ1); 6.01(75)(100); 5.52(60)(1İ01); 4.965(55)(011); 4.198(67)(1İ1İ1); 4.055(65)(110); 3.120(55)(021); 2.896(60)(21İ1,003,2İ20). The crystal structure was solved by direct methods from single-crystal X-ray diffraction data and refined to R = 0.0737. The yaroshevskite structure is unique. It is based on corrugated layers made up of chains of edge-sharing flat squares with central Cu2+ cations [Cu(1), Cu(4) and Cu(5)]; neighbouring chains are connected via groups consisting of three Cu2+-centred squares [two Cu(3) and Cu(6)]. Neighbouring layers are connected via pairs of Cu(2)O4Cl five-coordinate polyhedra and isolated VO4 tetrahedra. The structure of yaroshevskite can also be considered in terms of oxygen-centred tetrahedra: O(7)Cu4 tetrahedra are connected via common Cu(4) and Cu(5) vertices to form pyroxene-like chains [O2Cu6]∞. In this context, the structural formula can be written Cu3[O2Cu6][VO4]4Cl2. The mineral name honours the Russian geochemist Alexei A. Yaroshevsky (b. 1934) of Moscow State University.