Fluorine-containing borate crystal materials are particularly attractive due to their rich structural chemistry and excellent properties for optical applications. In this work, a new compound Ba3.75MgB7O14F2.5 has been synthesized through the high-temperature solution method. In the crystal structure of Ba3.75MgB7O14F2.5, the [B7O14] basic building unit and the [MgO3F3] octahedra are interconnected to create a complex three-dimensional network. The structural feature of the less commonly observed [B7O14] units is discussed, and it has been found that such units in Ba3.75MgB7O14F2.5 are most conducive to achieving large birefringence. In addition, Ba3.75MgB7O14F2.5 exhibits good thermal stability, a short ultraviolet cutoff of 203 nm, and large birefringence (0.081@546 nm), indicating its potential as a new UV birefringent crystal.