New quaternary lithium - d(0) cation - lone-pair oxides, Li-6(Mo2O5)(3)(SeO3)(6) (Pmn2(1)) and Li-2(MO3)(TeO3) (P2(1)/n) (M = Mo6+ or W6+), have been synthesized and characterized. The former is noncentrosymmetric and polar, whereas the latter is centrosymmetric. Their crystal structures exhibit zigzag anionic layers composed of distorted MO6 and asymmetric AO(3) (A = Se4+ or Te4+) polyhedra. The anionic layers stack along a 2-fold screw axis and are separated by Li+ cations. Powder SHG measurements on Li-6(Mo2O5)(3)(SeO3)(6) using 1064 nm radiation reveal a SHG efficiency of approximately 170 X alpha-SiO2. Particle size vs SHG efficiency measurements indicate Li-6(Mo2O5)(3)(SeO3)(6) is type 1 nonphase-matchable. Converse piezoelectric measurements result in a d(33) value of similar to 28 pm/V and pyroelectric measurements reveal a pyroelectric coefficient of -0.43 mu C/m(2)K at 50 degrees C for Li-6(Mo2O5)(3)(SeO3)(6). Frequency dependent polarization measurements confirm that Li-6(Mo2O5)(3)(SeO3)(6) is nonferroelectric, i.e., the macroscopic polarization is not reversible, or 'switchable'. Infrared, UV-vis, thermogravimetric, and differential thermal analysis measurements and electron localization function calculations were also done for all materials.