In light of ever growing interests in noncentrosym. materials, a fascinating reticular chem. is illustrated via the structure of a new family of solids where the acentric symmetry of the known [V4+14As3+8O42Cl]5- POM cluster is manifested through the network construction of countercations featuring slabs of Cs+-based half SOD β-cages. The synthesis of Cs5V14As8O42X (X = Cl, Br, I; 1-3, resp.) and their hydrates (4-6) and of a decompn. product Cs5V14As2O40Cl·2.6H2O (7) is described and their crystal structures detd. The non-linear optical properties of 1-3 are described and SHG measurements show efficiencies of 1-3 comparable with α-SiO2.