A transition-metal free green procedure for the synthesis of a highly valuable class of heteroaromatics, quinazolines, was developed by using easily available 2-aminobenzylamines and α,α,α-trihalotoluenes. Quinazoline is one of the highly valuable classes of fused heteroaromatics that is prevalent in numerous bioactive natural products, alkaloids, and life-saving synthetic pharmaceuticals. A variety of 2-aryl quinazolines are formed smoothly in the presence of only sodium hydroxide and molecular oxygen in water at 100 °C. The crystallization process of the crude reaction mixture for the purification of the solid products avoids huge solvent consuming work-up and column chromatographic techniques, which make the overall process more sustainable and economical.