Brown needle-like crystals of the compound Ba(VOSeOH), prepared by hydrothermal synthesis at 180° for five days, were characterized by single crystal X-ray diffraction. The structure is monoclinic P2c with a = 10.803(2), b = 5.1126(8), c = 17.905(3) Å β = 92.048(2)° V = 988.2(5) Å 3 Z = 4, ρ = 3.865 gcm-3 M = 575.14, R = 0.038, R = 0.0389 for 3681 observed, independent reflections with I > 2σ(I), measured at 150 K. The structure contains a complex three-dimensional network of VO VO SeO and BaO polyhedra, linked into chains along [101], with coordinated water molecules in the spaces between chains. The chains contain pairs of V + octahedra sharing an edge (V 0 dimers), and pairs of V 5+ square pyramids also sharing an edge (V dimers), with the dimers connected to each other by barium-centered, mono-capped square antiprisms and SeO trigonal pyramids. The chains are linked to each other via-V-O-Se- ,-V-O-Ba-and-Ba-O-Se-bonds with Se coordinated to oxygen at distances of 1.669(4) to 1.748(4) Å which is typical for Se(IV) with a lone pair of electrons occupying the fourth coordination position in the pseudotetrahedral SeO-group. The structural features and interchain arrangement of the title compound are similar to the related, interlayer compounds VOSeOH (1) and Ba(VOSeOHSeO) (2) described previously.