Single crystals of lithium zinc vanadate, LiZnVO4, were grown by the flux method. The structural type of this vanadate is characterized by a three-dimensional arrangement of tetrahedra sharing apices in an LiZnVO4 network. This arrangement contains three different tetrahedra, namely one [VO4] and two disordered mixed-site [Li/ZnO4] tetrahedra. The resulting lattice gives rise to hexagonal channels running along the [0001] direction. Both sites in the mixed-site [Li/ZnO4] tetrahedra are occupied by a statistical mixture of lithium and zinc with a 1:1 ratio. Therefore, LiZnVO4 appears to be the first vanadate known to crystallize with a disordered phenacite structure. Moreover, the resulting values of calculated bond valences (Li = 1.083, Zn = 2.062 and V = 5.185) tend to confirm the structural model