The present work emphasizes catalyst‐free 2,4,5‐tri‐ and 1,2,4,5‐tetra substituted imidazole synthesis using diversified aldehydes with benzil, ammonium acetate, or amines. Ammonium acetate plays a vital role as a reactant catalyst by dissociating into acetic acid to afford imine and diamine formation to ascertain the 2,4,5‐tri‐ and 1,2,4,5‐tetra substituted imidazoles. The key advantages of the current approach are efficient, greener, eco‐friendly, and facile, with moderate to excellent yield in shorter reaction time at the temperature of 80°C. Ethanol:water as a solvent makes the reaction process eco‐friendly. Overall, the described approach offers a promising route for the efficient and sustainable synthesis of substituted imidazoles, which have a wide range of applications in various fields, including pharmaceuticals, agrochemicals, and materials science.