Protocaseyite, [Al4(OH)6(H2O)12][V10O28]·8H2O, is a new mineral (IMA2020-090) occurring in low-temperature, post-mining, secondary mineral assemblages at the Burro mine, Slick Rock district, San Miguel County, Colorado, U.S.A. Crystals of protocaseyite are saffron-yellow, thick blades, with pale orange-yellow streak, vitreous luster, brittle tenacity, curved fracture, two very good cleavages, a Mohs hardness of 2, and a density of 2.45(2) g/cm3. The optical properties of protocaseyite could be only partly determined: biaxial with α = 1.755(5), β < 1.80, γ > 1.80 (white light); pleochroic with X and Y yellow, Z orange (X ≈ Y < Z). Electron-probe microanalysis and crystal-structure solution and refinement provided the empirical formula [(Al3.89Mg0.11Ca0.02)Σ4.02(OH)6(H2O)12][H0.06V10O28]·8H2O. Protocaseyite is triclinic, P1, a = 9.435(2), b = 10.742(3), c = 11.205(3) Å, α = 75.395(7), β = 71.057(10), γ = 81.286(6)°, V = 1036.4(5) Å3, and Z = 1. The crystal structure (R1 = 0.026 for 4032 Io>2 σI reflections) contains both the [V10O28]6− decavanadate polyoxoanion and a novel [Al4(OH)6(H2O)12]6+ polyoxocation.