Based on the combined experimental and theoretical data, we suggest a stepwise deoxygenation mechanism from the alcohol under standard reaction conditions (Figure ). Initial cathodic singleelectron reduction of the alcohol 1 results in a radical anion with the unpaired electron primarily residing in the ipso-and para-positions of the aromatic ring (for spin density calculations, see Section 12 in the ESI). Subsequent anionic C-OH bond cleavage results in a radical intermediate that rearomatizes to the benzylic radical 1'. A second electron transfer results in a radical-polar crossover event and the formation of benzylic carbanion 1'' that undergoes protonation to furnish the alkane product 2 or undergoes coupling with CO2 to form aryl acetic acid 4. As anodic counter reaction, borohydride is oxidized to H2 and boron-based side-products.