A binary mixture of organic salts, also known as ionic liquids, [C12mim][Br]:[MPIM][HCOO] denoted as BmIL1 has been ex‐plored as bifunctional catalyst for the selective synthesis of 2 ‐phenylquinazolin‐4(3H)‐ones and 2,3‐dihydroquinazolin‐(1H)‐ones from same precursors under metal, ligand and additive free conditions. The methodology has been extended to the synthesis of 2‐phenylquinazolin‐4(3H)‐ones via another pathway from different precursors under the same catalytic system. Greener synthesis of existing drugs reestablished the multifunctionality of BmIL1. Gram scale synthesis of both the products, DFT calculations and sc‐XRD data add significance to the developed protocol. Moreover, high atom economy and eco‐scale values justify the sustainability of the methodology.