Ultraviolet (UV) nonlinear optical (NLO) crystals are essential for advancing laser-based technologies in the UV region. However, overcoming the inherent trade-off between nonlinearity and bandgap in UV NLO materials remains a fundamental challenge. Herein, we propose an innovative molecular design strategy employing 5-hydroxy-2-pyridinecarboxylic acid as a novel molecular motif, characterized by its moderate π-conjugated, multidentate coordination capability, and low toxicity. By combining this organic ligand with alkali metals, we successfully obtained a noncentrosymmetric hybrid crystal, Na2(C6H4NO3)2∙H2O. This compound achieves an exceptional combination of a strong phase-matched second-harmonic generation response (6.2 × KDP), large birefringence (0.394), and a short UV cutoff edge (282 nm), effectively mitigating typical performance limitations. This work not only provides a promising candidate for UV laser applications but also demonstrates an effective strategy for designing high-performance hybrid crystals for coherent UV light generation.