Red-brown crystals of a new mixed alkali oxo sulfato vanadium(V) compound Na2K6(VO)(2)(SO4)(7), suitable for X-ray determination, have been obtained from the catalytically important binary molten salt system M2S2O7-V2O5 (M = 80% K and 20% Na). By slow cooling of a mixture with the mole fraction X-V2O5 = 0.24 from 325 degreesC, i.e., just below the liquidus temperature, to the solidus temperature of around 300 degreesC, a dark reddish amorphous phase was obtained containing crystals of the earlier described V(V)-V(IV) mixed valence compound K-6(VO)(4)(SO4)(8) and Na2K6-(VO)(2)(SO4)(7) described here. This compound crystallizes in the tetragonal space group P4(3)2(1)2 (No. 96) with a = 9.540(3) Angstrom, c = 29.551(5) Angstrom at 20 degreesC and Z = 4. It contains a distorted VO6 octahedron with a short V-O bond of 1.552(6) Angstrom, a long one of 2.276(5) Angstrom trans to this, and four equatorial V-O bonds in the range 1.881(6)-1.960-(6) A. The deformation of the VO6 octahedron is less pronounced compared to that of the known oxo sulfato V(V) compounds. Each VO3+ group is coordinated to five sulfate groups of which two are unidentately coordinated and three are bidentate bridging to neighboring VO3+ groups. The length of the S-O bonds in the S-O-V bridges of the two unidentately coordinated sulfato groups are 1.551(6) Angstrom and 1.568(6) Angstrom, respectively, which are unusually long compared to our earlier measurements of sulfate groups in other V(111), V(IV), and V(V) compounds.