The most advanced UV-vis and IR NLO materials are usually borates and chalcogenides, respectively. But thioborates, especially thio-borometalates, are extremely rare. Here, four new such compounds are discovered by solid state reactions representing 0D structures constructed by isolated BQ(3) trigonal planes and discrete MQ(3) pyramids with Ba2+ cations filling among them, centrosymmetric monoclinic P2(1)/c Ba-3(BS3)(1.5)(MS3)(0.5) (M = Sb, Bi) 1, 2 with a = 12.9255(9), 12.946(2) angstrom; b = 21.139(2), 21.170(2)angstrom; c = 8.4194(6), 8.4207(8) angstrom; beta = 101.739(5), 101.688(7)degrees; V = 2252.3(3), 2259.9(3) angstrom(3) and noncentrosymmetric hexagonal P (6) over bar 2m Ba-3(BQ(3))(SbQ(3)) (Q = S, Se) 3, 4 with a = b = 17.0560(9), 17.720(4) angstrom; c = 10.9040(9), 11.251(3) angstrom; V = 2747.1(3), 3060(2) angstrom(3). 3 exhibits the strongest SHG among thioborates that is about three times that of the benchmark AgGaS2 at 2.05 mu m. 1 and 3 also show an interesting structure relationship correlated to the size mismatching of the anionic building units that can be controlled by the experimental loading ratio of B:Sb. Syntheses, structure characterizations, and electronic structures based on the density functional theory calculations are reported.