A novel and straightforward approach for synthesizing quinazolinones and quinazoline derivatives employing sulfur‐mediated annulative coupling of 2‐aminobenzamides and 2‐aminobenzylamines in conjunction with sulfoxonium ylides has been described. This method demonstrates a broad substrate range and exhibits excellent tolerance towards various functional groups. Finally, this protocol has been successfully applied to synthesize pyrazino‐fused quinazolinone derivative with adjustable fluorescence properties and tryptanthrin, a compound known for its potent antitubercular activity.