Acetylacetone (2,4-pentanedione, 1) is a molecule whose tautomeric forms are in dynamic equilibrium. Concentrated salt solutions in nonaqueous solvents exert a remarkable influence on the keto-enol ratio of this beta-diketone. The keto content of 1 increases from 5% in pure diethyl ether to 84.5% in a 4.14 M lithium perchlorate-diethyl ether (LPDE) solution, a nearly 17-fold increase. The equilibrium expression, K = [keto]/[enol] = k(f)/k(r), exhibits a linear dependence on [LiClO4], with the formal order of participation of lithium ion in the equilibrium being 1.0. A kinetic analysis reveals that k(f) is independent of LPDE concentration, whereas k(r) displays an inverse dependence on salt concentration, indicating preferential coordination of the keto tautomer with Li+. Although 1 exits as the enol in water only to the extent of 16%, the addition of lithium perchlorate further reduces this figure. In an aqueous 4.02 M LiClO4 solution, acetylacetone enol accounts for only 4.6% of the total amount of 2,4-pentanedione present. It has also been found that acetylacetone itself is an excellent solvent for LiClO4 as well as for NaClO4 with solutions containing up to 7.5 M LiClO4 attainable. The enol content of 1 decreases dramatically from 81% to 7.4% on going from the neat liquid to a solution of 6.39 M LiClO4 in acetylacetone.