The discovery of novel organic−inorganic hybrid nonlinear optical (NLO) crystal materials holds great potential in advancing laser science and technology as they offer a wide range of benefits including easy synthesis, structural versatility, and high hyperpolarizability. Herein, the integration of L-tartaric acid (L-C 4 H 6 O 6 ) and ZnSO 4 gave rise to two acentric Zn-based organic− inorganic hybrid crystals, namely, Zn 2 (, water molecule, or [SO 4 ] tetrahedron. Interestingly, they possess moderate secondorder NLO effects of 0.28 × KH 2 PO 4 (Zn-LT) and 0.57 × KH 2 PO 4 (Zn-LTS), large birefringence of 0.075 (Zn-LT) and 0.069 (Zn-LTS), suggesting that the introduction of [SO 4 ] groups with intrinsically weak polarizability and weak optical anisotropy induces the enhancement of the NLO effect while without reducing birefringence much. In addition, both of them display UV cutoff edges near 210 nm, indicating their potential as NLO crystals applied in the UV and solar-blind region.