The zero-order waveplates, the essential materials in altering the polarization state of optical waves, are significant in polarimetry and the laser industry. Restricted by birefringence and absorption edge, few materials can have moderately small birefringence (Δn < 0.01) and a deep-ultraviolet (DUV; λ < 200 nm) transparency range. We used the B 3 O 3 F 6 unit for designing the zero-order waveplate material, which is composed of three BO 2 F 2 tetrahedra interconnected by corner sharing. Here we obtained a new Cs 3 B 3 O 3 F 6 compound with the isolated B 3 O 3 F 6 unit by a high-temperature solution method, which has the DUV cutoff edge and suitable birefringence (0.0069 at 532 nm) based on the experimental and computational results. This demonstrates that the isolated B 3 O 3 F 6 unit is a potential group, which favors the search for suitable compounds for DUV zero-order waveplate materials.