Charge-assisted hydrogen bonds (CAHBs) play critical roles in many systems from biology through to materials. In none of these areas has the role and function of CAHBs been explored satisfactorily because of the lack of data on the energy of CAHBs in the condensed phases. We have, for the first time, quantified three types of CAHBs in both the condensed and gas phases for 1-(2'-hydroxylethyl)-3-methylimidazolium acetate ([C(2)OHmim][OAc]). The energy of conventional OH center dot center dot center dot[OAc](-) CAHBs is similar to 10 kcal. mol(-1), whereas nonconventional C(sp2)H center dot[OAc](-) and C(sp3)H center dot center dot center dot[OAc](-) CAHBs are weaker by similar to 5-7 kcal.mol(-1). In the gas phase, the strength of the nonconventional CAHBs is doubled, whereas the conventional CAHBs are strengthened by <20%. The influence of cooperativity effects on the ability of the [OAc](-) anion to deprotonate the imidazolium cation is evaluated. The ability to quantify CAHBs in the condensed phase on the basis of easier accessible gas-phase estimates is highlighted.