Three new cadmium(II) tartratoborates, namely, Cd-5[(C4H2O6)(2)B](2)(H2O)(8)center dot 3H(2)O (1), K2Cd4[(C4H2O6)(2)B](2) (H2O)(2) (2), and Li0.92K1.08Cd1.5 [(C4H2O6)(2)B](H2O)(2) (3), have been successfully synthesized by the hydrothermal method. Compounds 1-3 belong to centric C2/c, acentric Pc, and the polar C2, respectively. Through based on the same hybrid borate-tartrate [(C4H2O6)(2)B](5-) anions, they exhibit different structures. The [(C4H2O6)(2)B](5-) anion is composed of two tartrate anions and a B(OH)(4)(-) unit. Compound 1 features a novel 3D network formed by 2D {Cd-3[(C4H2O6)(2)B](2)(H2O)(2)}(4-) anionic layers and [Cd2O10] dimers, forming tunnels of large 14-MRs which are filled by the non-coordination water molecules. Compound 2 has a characteristic 3D network based on {Cd-2[(C4H2O6)(2)B]}(-) unit interlinked via carboxylate groups, forming tunnels of 11-MRs, half of which stuffed with the K+ ions. Compound 3 features 2D {Cd-4[(C4H2O6)(4)B]}(3+) layers which are separated by K/Li ions. Luminescent studies suggest that they emit blue light. Compounds 2 and 3 display phase-matchable second harmonic generation signs of about 3.2x and 1.5X KH2PO4, respectively.