Tapiaite (IMA2014-024), Ca5Al2(AsO4)4(OH)4·12H2O, is a new mineral from the Jote mine, Tierra Amarilla, Copiapó Province, Atacama, Chile. The mineral is a late-stage, low-temperature, secondary mineral occurring with conichalcite, joteite, mansfieldite, pharmacoalumite, pharmacosiderite and scorodite in narrow seams and vughs in the oxidized upper portion of a hydrothermal sulfide vein hosted by volcanoclastic rocks. Crystals occur as colourless blades, flattened on {101} and elongated and striated along [010], up to ∼0.5 mm long, and exhibiting the forms {101}, {101} and {111}. The blades are commonly intergrown in subparallel bundles and less commonly in sprays. The mineral is transparent and has a white streak and vitreous lustre. The Mohs hardness is estimated to be between 2 and 3, the tenacity is brittle, and the fracture is splintery. It has two perfect cleavages on {101} and {101}. The calculated density based on the empirical formula is 2.681 g cm–3. It is optically biaxial (+) with α = 1.579(1), β = 1.588(1), γ = 1.610(1) (white light), 2Vmeas = 66(2)° and 2Vcalc = 66°. The mineral exhibits no dispersion. The optical orientation is X ≈ [101]; Y = b, Z ≈ [101]. The electron-microprobe analyses (average of five) provided: Na2O 0.09, CaO 24.96, CuO 0.73, Al2O3 10.08, Fe2O3 0.19, As2O5 40.98, Sb2O5 0.09, H2 O 23.46 (structure), total 100.58 wt.%. In terms of the structure, the empirical formula (based on 32 O a.p.f.u.) is (Ca4.83Cu0.102+Na0.03)Σ4.96(Al2.14Fe0.033+)Σ2.17[(As3.875+Sb0.015+)Σ3.88O16][(OH)3.76(H2O)0.24]Σ4(H2O)10·2H2O. The mineral is easily soluble in RT dilute HCl. Tapiaite is monoclinic, P21/n, with unit-cell parameters a = 16.016(1), b = 5.7781(3), c = 16.341(1) Å, β = 116.704(8)°, V = 1350.9(2) Å3 and Z = 2. The eight strongest lines in the powder X-ray diffraction pattern are [dobs Å(I)(hkl)]: 13.91(100)(101), 7.23(17)(200,002), 5.39(22)(110,011), 4.64(33)(112,211,303), 3.952(42)(113,311,213), 3.290(35)(214,412,114,411), 2.823(39)(303,315) and 2.753(15)(513,115,121,511). The structure of tapiaite (R1 = 5.37% for 1733 Fo > 4σF) contains Al(AsO4)(OH)2 chains of octahedra and tetrahedra that are topologically identical to the chain in the structure of linarite. CaO8 polyhedra condense to the chains, forming columns, which are decorated with additional peripheral AsO4 tetrahedra. The CaO8 polyhedra in adjacent columns link to one another by corner-sharing to form thick layers parallel to {101} and the peripheral AsO4 tetrahedra link to CaO6 octahedra in the interlayer region, resulting in a framework structure.