Imidazolium compounds are very versatile molecules that have enabled a large number of recent innovations in the field of chemistry. Among these, imidazolium-based ionic liquids (ILs) are the most prominent. Coming with beneficial solvent properties, negligible vapor pressure and high thermal stability, ILs are often classified as "green solvents". [1] A critical analysis, however, reveals that ILs synthesis and purification show a lot of room for improvement in terms of sustainability and cost reduction. This is particularly true for the so-called "task specific" ionic liquids, compounds in which the imidazolium cation has been additionally manipulated to include one or more reactive functionalities. [2] Consequently, greener methods to access ILs are still highly welcomed and are expected to expand the application range of those systems. Traditionally, heterosubstituted imidazolium scaffolds have been targeted by following the general idea that asymmetric substitution results in ILs with lower melting points. Double alkylation of imidazoles [3] has been successfully employed as a strategy for the preparation of cations decorated with hydroxyl groups, [4] thiol groups, [5] alkene groups, [6] and others. [2] Despite their popularity, quaternization reactions and the following functionalization steps are responsible for the relatively long syntheses, often characterized by high temperatures and long reaction times, accompanied by low-yielding purification procedures, [7] with the discussed implications on production costs and sustainability. Interestingly, imidazolium compounds can be easily accessed by simple modifications of the Debus-Radziszewski synthesis. [8] This convenient one-pot approach involves reaction of a primary amine, formaldehyde, and a 1,2-dicarbonyl compound, the only drawback being its limitation to the formation of homosubstituted species. Such imidazolium cations have been extensively reported, [9] but a systematic study on their properties in ILs is still missing. Besides the field of ILs, advancement in the synthesis of 1,3-homosubstituted imidazolium cations can additionally foster the development of other areas of chemistry, such as polyionic liquids (PILs), [10] N-heterocyclic carbenes, [11] antifungal drugs, [12] and carbon materials. [13] In this paper, we report a general strategy for the synthesis of symmetric, bifunctional imidazolium ionic compounds derived from readily available and sustainable starting materials, including carbohydrate fragments and simple amino acids/amines. Recently, imidazolium-based room temperature ILs with amino acids as the counterions were presented. [14] Here, we surmised that the amino group of natural amino acids could react in a Debus-Radziszewski-like reaction, thereby providing the resulting imidazolium ions with the well-known set of biological functionalities, depending on the amino acid exploited. We focused our investigation on the use of pyruvaldehyde as the 1,2-dicarbonyl scaffold instead of the commonly used glyoxal. Pyruvaldehyde has been ...