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 π‐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, Ba3(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.