The crystal structure of khinite, Pb2+Cu32+ Te6+O6(OH)2, orthorhombic, a = 5.7491(10), b = 10.0176(14), c = 24.022(3) Å, V = 1383.6(4) Å3, space group Fdd2, Z = 8, Dcalc = 6.29 g/cm3, from the Empire mine, Tombstone, Arizona, USA, has been solved by direct methods and refined to R1 = 3.2% on the basis of 636 unique observed reflections. There is one distinct Te site occupied by Te and coordinated by six O atoms in an octahedral arrangement with a <Te–O> distance of 1.962 Å, typical of Te6+. There are three octahedrally-coordinated Cu sites, each of which is occupied by Cu2+ with <Cu–O> distances of 2.132, 2.151 and 2.308 Å, respectively. Each Cu octahedron shows four short meridional bonds (~1.95 Å) and two long apical bonds (2.46–2.99 Å) characteristic of Jahn-Teller-distorted Cu2+ octahedra. There is one distinct Pb site occupied by Pb and coordinated by six O atoms and two (OH) groups with a <Pb–O, OH> distance of 2.690 Å. TeΦ6 and CuΦ6 octahedra share edges and corners to form an [MΦ2] (where Φ = O, OH) layer of composition [TeCu3Φ8]. These layers stack along the c axis at 6 Å intervals with Pb atoms between the layers. Identical layers occur in the structure of parakhinite, Pb2+Cu32+ Te6+O6(OH)2, hexagonal, a = 5.765(2), c = 18.001(9) Å, V = 518.0(4) Å 3, space group P32, Z = 3, Dcalc = 6.30 g/cm3. It is only the relative stacking of the TeCu3Φ8 layers in the c direction that distinguishes the two structures, and hence khinite and parakhinite are polytypes.