The utilization of N,N-dimethylbenzimidazolium iodide as a catalyst in [Bmim]BF4 for benzoin condensation under microwave irradiation demonstrates its efficiency and eco-friendliness. This method enables the synthesis of α-hydroxy carbonyl compounds from various aromatic and heteroaromatic aldehydes with significant yields, ranging from good to high (89-96%). The reactions proceed swiftly, yielding no detectable byproducts. Moreover, the recycled reaction media, comprising benzimidazolium salt and NaOH after extraction, can be reused multiple times without a significant loss of efficiency.