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A "three‐components" supramolecular assembly has been fabricated by mixing 2, 2': 6', 2"‐terpyridine attached pillar[5]arene, cyano and triazole bearing alkyl chain and Zn2+ in solvent of CHCl3 and CH3CN. The driving forces for the assembly were believed to be host‐guest and metal chelating interactions as characterized by 1H NMR, UV‐vis and fluorescence spectra. The supramolecular organo‐gel formed upon the concentration of components amount to 1 M. The supramolecular displayed nitrobenzene based explosive sensing capability using picric acid, ortho‐nitrobenzene and phenol as samples. The assembly was most sensitive towards picric acid among the three analytes. The limit of detection for picric acid was determined to be 1.66 × 10−4 M. [ABSTRACT FROM AUTHOR]