The crystal structure of vlodavetsite, AlCa₂(SO₄)₂F₂Cl·4H₂O, has been determined, space group I4/m, a = 6.870(1), c = 13.342(2) Å, Z = 2, D_x = 2.35 g/cm³. The polyhedron cation chains are parallel to [001] and consist of couples of distorted Ca octahedra alternating with one distorted Al octahedron rotated through 24° with respect to the former. The chains are linked by SO₄-tetrahedra so that all of the four tetrahedron oxygen atoms take part in coordination of Ca atoms to form a distorted octahedron with Cl and F atoms. The Al coordination polyhedron consists of two F atoms and four oxygen atoms belonging to water molecules. There is a specific interaction via hydrogen bonds between oxygen atoms of SO₄-tetrahedra and water molecules.