In nucleophilic fluorination reactions, developing strategies for tuning the reactivity profile of fluoride anion in organic solution is a major challenge. Inspired by Nature¿s biosynthetic approach with the fluorinase enzyme system and by early work using tertiary alcohol solvents, we have studied the effect of intermolecular hydrogen bonding on the reactivity profile of fluoride anion with the goal of developing superior fluoride reagents for synthetic applications. Through a combination of reactivity data, solid-state characterization of [OH¿¿¿F] complexes, and computational analysis, we have gained new insights into the characteristics of optimal hydrogen bond donors and have identified highly reactive alcohol hydrogen-bond donor motifs. To advance this study, we propose a single-crystal neutron diffraction study to determine precisely the hydrogen positions.