Alkali-metal salts of 9,10-dimethyl-9,10-dihydro-9,10-diboraanthrancene (M2[DBA-Me2]; M+ = Li+, Na+, K+) activate the H–B bond of pinacolborane (HBpin) in THF already at room temperature. For M+ = Na+, K+, the addition products M2[4] are formed, which contain one new H–B and one new B–Bpin bond; for M+ = Li+, the H– ion is instantaneously transferred from the DBA-Me2 unit to another equivalent of HBpin to afford Li[5]. Although Li[5] might commonly be considered a [Bpin]– adduct of neutral DBA-Me2, it donates a [Bpin]+ cation to Li[SiPh3], generating the silyl borane Ph3Si–Bpin; Li2[DBA-Me2] with an aromatic central B2C4 ring acts as the leaving group. Furthermore, Li2[DBA-Me2] catalyzes the hydroboration of various unsaturated substrates with HBpin in THF. Quantum-chemical calculations complemented by in situ NMR spectroscopy revealed two different mechanistic scenarios that are governed by the steric demand of the substrate used: In the case of the bulky Ph(H)C=NtBu, the reaction requires elevated temperatures of 100 °C, starts with H–Bpin activation which subsequently generates Li[BH4], so that the mechanism eventually turns into “hidden borohydride catalysis”. Ph(H)C=NPh, Ph2C=O, Ph2C=CH2, and iPrN=C=NiPr undergo hydroboration already at room temperature. Here, the active hydroboration catalyst is the [4+2] cycloadduct between the respective substrate and Li2[DBA-Me2]: In the key step, attack of HBpin on the bridging unit opens the bicyclo[2.2.2]octadiene scaffold and gives the activated HBpin adduct of the Lewis-basic moiety that was previously coordinated to the DBA-B atom.