Crystals of copper-doped barium fluoride borate solid solutions Ba 3 (BO 3 ) 2-x F 3x :Cu were grown from high-temperature solution. Using X-ray single-crystal diffraction, the structure was solved and refined in Pbam space group. These crystals are colored in brown, revealing linear dichroism. Optical and electron spin resonance spectroscopic investigations concluded that the light absorption of Ba 3 (BO 3 ) 2-x F 3x :Cu crystals is caused by both the exciton and free charge carriers. This phenomenon is similar to those observed in other colored "antizeolites" built with the positively charged framework of porous [Ba 12 (BO 3 ) 6 ] 6+ building blocks (hence named as antizeolites). The coloring of Ba 3 (BO 3 ) 2-x F 3x :Cu crystals is associated with the absorption of Cu 2+ ions as well. For the first time, constants of the hyperfine interaction of copper ions Cu 2+ in octahedral fluorine surroundings [CuF 6 ] 4- have been determined.