Birefringent materials, which can modulate the polarization of light, are almost exclusively limited to oxides. Peroxides have long been overlooked as birefringent materials, because they are usually not stable in air. Now, the first peroxide birefringent material Rb₂VO(O₂)₂ F is reported, the single crystals of which keep transparency after being exposed in the air for two weeks. Interestingly, Rb₂VO(O₂)₂ F does not feature an optimal anisotropic structure, but its birefringence (Deltan=0.189 at 546nm) exceeds those of the majority of oxides. According to the first-principles calculations, this exceptional birefringence should be attributed to the strong electronic interactions between localized pi orbital of O₂^2- anions and V⁵⁺ 3d orbitals, which may be also favorable to the stability in the air for Rb₂ VO(O₂)₂ F. These findings distinguish peroxides as a brand-new class of birefringent materials that may possess birefringence superior to the traditional oxides.