Herein, we report a multicomponent reaction for the efficient synthesis of polysubstituted 2H‐imidazoles from readily available 1,2‐diketones, ketones, and ammonium acetate under transition‐metal‐free conditions. Both nitrogen atoms in the resulting 2H‐imidazole products are derived from the cost‐effective inorganic ammonium acetate. This protocol achieves the cleavage of three C–O bonds and the formation of four C–N bonds in a single operation. The advantages of this protocol include low cost, broad substrate scope, good functional group tolerance, and high atom‐ and step‐economy.