Employing salt-inclusion chem., we have developed a new class of hybrid solids based on transition-metal-contg. silicate, phosphate, and arsenate systems which have resulted in a large no. of novel solids that exhibit fascinating nanostructures of magnetic, electronic and catalytic importance. In an expanded effort by substituting oxyanions with vanadates, we have isolated two new transition metal (II) meta-vanadate compds. using high-temp. flux methods in molten salt media. The title compds. (CsCl)2M(VO3)2 (M = Mn, Cu) crystallize in an orthorhombic space group Cmm2 (no. 35) and tetragonal space group P4122 resp. The X-ray single crystal structure reveals that the extended lattice of the Mn2+ compd. consists of a meta-vanadate chain propagating along the a axis; whereas, the Cu2+ phase exhibits two nonintersecting, orthogonal chains along the a and b axes. It is also revealed that in both lattices, the M2+ cations adopt an octahedral (MO2Cl4) coordination. However, the Mn2+ compd. exhibits the (100) ReO3-type octahedral slabs propagating along the ac plane, while Cu2+ consists of isolated octahedra. Furthermore, the parallel slabs in the former are interlinked through sharing corner oxygen atoms with the meta-vanadate chains along b. In the latter, however, the Cu2+ cations can be considered as linkers to bridge the orthogonal vanadate chains via sharing corner oxygen atoms of the polyhedra. Due to the versatility of the MO2Cl4 and the VO4 units, these two isomorphous compds. form two different channel structures that posses 5 & 14-memebered ring windows, resp. Given the structural flexibility and the demonstrated utilities of salt, we anticipate more vanadates having novel nanostructures to come. In this presentation, we will discuss the results of the detailed solid state synthesis, crystal growth, and correlation studies of structure and magnetic property anal.