Although phosphates are a rich source of deep-ultraviolet optical materials, the realization of large optical anisotropy in them still remains a challenge because of the small polarizability anisotropy of [PO4] units. Inspired by the fluoridation strategy and hydrogen bond interaction, a new metal-free monofluorophosphate, (N2H6)[HPO3F](2), was synthesized, which exhibits a large birefringence (cal. 0.077) and wide band gap (similar to 6.51 eV). Such a large birefringence in (N2H6)[HPO3F](2) sets a new record among available fluorophosphates, and the [HPO3F] unit is theoretically confirmed to be a new birefringence-active unit.