<p>Fluoroborane-type molecules (R¹R²B–F) are of interest in synthetic chemistry, but to date, apart from a handful of small species (such as H₂BF, HBF₂ , and BF₃), little is known concerning the effect of substituents in governing the strength of the B–F bonds of such species toward homolytic dissociation in the gas phase. In this study, we have calculated the bond dissociation enthalpies (BDEs) of thirty unique B–F bonds at the CCSD(T)/CBS level using the high-level W1w thermochemical protocol. The B–F bonds in all species considered are very strong, ranging from 545.9 kJ mol⁻¹ in (H₂B)₂B–F to 729.2 kJ mol⁻¹ HBF₂. Nevertheless, these BDEs still vary over a wide range of 183.3 kJ mol⁻¹. The structural properties that affect the BDEs are examined in detail, and the homolytic BDEs are rationalized based on molecule stabilization enthalpies and radical stabilization enthalpies. Since polar B–F bonds may represent a challenging test case for density functional theory (DFT) methods, we proceed to examine the performance of a wide range of DFT methods across the rungs of Jacob's Ladder for their ability to compute B–F BDEs. We find that only a handful of DFT methods can reproduce the CCSD(T)/CBS BDEs with mean absolute deviations (MADs) below the threshold of chemical accuracy (i.e., with average deviations below 4.2 kJ mol⁻¹). The only functionals capable of achieving this feat were (MADs given in parentheses): ωB97M-V (4.0), BMK (3.5), DSD-BLYP (3.8), and DSD-PBEB95 (1.8 kJ mol⁻¹).</p>