Improving taste and tuning physicochemical properties of active pharmaceutical ingredients (API) by forming new salts or cocrystals with an artificial sweetener, such as saccharine (Sac) and acesulfame (Acs), is an effective crystal engineering strategy for facilitating successful delivery of bitter drugs. However, the number of reported solid forms of Acs is curiously lower (29) than that of Sac (275). An analysis of the literature revealed that the preparation of salts or cocrystals of Acs was hindered by the difficulty and cost in preparing Acs free acid from commercially available potassium salt (Acs-K). Here, we evaluated the broad applicability of an anion exchange reaction for preparing Acs solid forms using nine model compounds. In all cases, we successfully prepared Acs crystals, based on single crystal structure determination, simply from ion exchange between Acs-K and corresponding salts. The proton transfer propensity, hydrogen-bonding pattern, and amide group keto-enol tautomerism in the Acs crystals are also discussed.