Two new borate halides, Pb6Ba2(BO3)5X (X = Cl, Br), have been synthesized by solid-state reactions and their structures determined by single-crystal X-ray diffraction. They are isostructural and feature 3D frameworks composed of alternate stacking of [PbBO] and [PbBOX] layers which are connected by 10-coordinated Ba atoms along the c direction. First-principles calculations show that both compounds have a large birefringence of 0.1582 and 0.1810 at 532 nm, respectively. The large birefringence originates from the strong optical anisotropies of the Pb(2+) cations and (BO3)(3-) groups based on the real-space atom-cutting analysis. The IR and UV-Vis-NIR diffuse reflectance spectroscopy, as well as thermal stability analyses of both compounds, were performed.