The crystal structure of the double copper(II) complex with borodicitric acid [Cu(H2O)5(C6H6O7)2B]+ · [(C6H6O7)2B]− · 5H2O of composition Cu[(C6H6O7)2B]2 · 10H2O has been studied by X-ray crystallography. The crystals are monoclinic, space group P21): a = 10.7852(2) Å, b = 9.9980(2) Å, c = 17.9500(5) Å; β = 101.126(1)°, FW = 1025.75, V = 1899.18(7) Å3, Z = 2. The dicitratoborate anions with a spirane structure have a normal geometry. The coordination polyhedron of the copper atoms is a distorted octahedron (CN 6 = 4 + 2) with an average equatorial Cu-O distance of 1.965 ± 0.023 Å. The axial positions in the CuO6 octahedron are occupied by a water molecule and an oxygen atom of one of the citrate ligands: Cu-O(5w), 2.430(3) Å; Cu-O(8), 2.382(3) Å. The crystals have an extended intricate system of hydrogen bonds consisting of 27 unique three-center O-H…O, O(w)…O, and O(w)…O(w’) bonds and four-center O(w)…O, O(w’) bonds with different structural functions.