The main commercially used birefringent oxides alpha-BaB2O4 and YVO4 have the birefringences of 0.12 and 0.22. We propose a targeted high-throughput screening system to search birefringence-active functional modules (FMs) and large birefringent materials. A series of pi-conjugated C-O units [C2O4](2-), [C2O6](2-), [C4O4](2-), and [C6O6](2-) are discovered to be birefringence-active FMs. Theoretical and experimental studies on the crystals with C-O units confirm the feasibility of strategy. Based on this, the C-O containing compounds ranging from deep-ultraviolet to near-infrared region with large birefringence from 0.1 to 1.35 are found, and most of them break through the birefringent limit of oxides. The (NH4)(2)C2O4.H2O crystal is grown and its experimental birefringence is 0.248 at 546 nm, which is identified as a promising UV birefringent crystal. The A-site cations play significant roles in optical properties by influencing the density and arrangement of the C-O units.