In contrast to the well-investigated halogen-containing borates and carbonates, very few halogen-containing borate carbonate compounds have been reported. Specifically, no example of borate carbonate fluoride has been synthesized successfully until now. Herein, the planar pi-conjugated units [BO3](3-) and [CO3](2-) and the F- ions are introduced simultaneously into one crystal structure resulting in the first borate carbonate fluoride, Ba-3(BO3)(CO3)F, by the high-temperature solution method in the atmosphere. Its structure features a hexagonal channel formed by the [BO3](3-) and [CO3](2-) units with the [F3Ba8](13+) trimers filled in the channel. Various characterizations including single crystal- and powder-XRD, EDX, IR, UV-vis-NIR, and TG-DSC, together with the first principles calculation have been carried out to verify the structure and fully understand the structure-property relationships.