A wide variety of interesting heterocyclic cyanoacetanilide derivatives were amalgamated via the interaction of the key precursor 2-Cyano-N-(4-(phenyl diazenyl) phenyl) acetamide (1) with salicylaldehyde, 2-Hydroxy-1-naphthaldehyde, phenacyl bromide, acetylacetone, benzoylacetone, malononitrile dimer, elemental sulfur under Gewald conditions, various diazonium salts and chalcone derivatives to yield innovative coumarins, pyrazolones, pyridinones, pyridines, thiazoles, thiophenes, hydrazone derivatives, pyrazolotriazine and triazolotriazine end products incorporating azobenzene nucleus. The skeletons of the innovatively created compounds were clarified by diverse spectroscopic methods such as FT-IR, mass spectroscopy and 1H NMR. In conclusion, the insecticidal efficiency of the newly output compounds was assessed against the cotton leafworm, Spodoptera littoralis under laboratory conditions. According to the observed LC50 and LC90 values, azobenzene derivatives 18c, 21c, 18b, 21b and 18d exhibit excellent toxic effects with LC50 values of 13.248, 15.554, 18.370, 21.777 and 25.845 ppm, respectively, and toxicity index being 82.82, 70.54, 59.73, 50.38 and 42.45%, respectively, comparing with the recommended, methomyl insecticide, lannate 90% SP which was the utmost active compound (the lowermost LC50 value, 10.972 ppm, toxicity index, 100%).