Benzothiazole and benzoxazole heterocyclic rings containing 1,4,5-trisubstituted-1,2,3-triazoles are well-known for their wide range of applications in pharmaceutical and medicinal chemistry, but their high-yielding metal-free selective synthesis has always remained challenging, as no comprehensive simple protocol has been outlined to date. Owing to their structural and medicinal importance, herein, we synthesized various benzothiazole and benzoxazole heterocyclic rings-containing 1,4,5-trisubstituted-1,2,3-triazoles in high to excellent yields with chemo-/regioselectivity from the library of benzothiazole/benzoxazole-ketones and aryl/alkyl-azides through the enolate-mediated organocatalytic azide-ketone [3+2]-cycloaddition at the ambient conditions for few hours. The commercial availability or quick synthesis of the starting materials and catalysts, diverse substrate scope, chemo-/regioselectivity of organo-click reaction, quick synthesis of pharmaceutically active known compounds and their analogues, and numerous medicinal applications of benzothiazole/benzoxazole-triazoles are the key attractions of this metal-free organo-click reaction.