Single crystals of nickel(II) divanadium(V) ditellurium(IV) decaoxide, NiV(2)Te(2)O(10), were synthesized via a transport reaction in sealed evacuated silica tubes. The compound crystallizes in the triclinic system (space group P-1). The Ni atoms are positioned in the 1c position on the inversion centre, while the V and Te atoms are in general positions 2i. The crystal structure is layered, the building units within a (010) layer being distorted VO(6) octahedra and NiO(6) octahedra. The metal-oxide layers are connected by distorted TeO(4)E square pyramids (E being the 5s(2) lone electron pair of Te(IV)) to form the framework. The structure contains corner-sharing NiO(6) octahedra, corner- and edge-sharing TeO(4)E square pyramids, and corner- and edge-sharing VO(6) octahedra. NiV(2)Te(2)O(10) is the first oxide containing all of the cations Ni(II), V(V) and Te(IV).