The new super bulky 2‐benzhydryl‐4,6‐dimethyl azide (2) was synthesized and used in click reaction for the synthesis of super‐bulky 1‐(2‐benzhydryl‐4,6‐dimethylphenyl)‐4‐phenyl‐1H‐1,2,3‐traizole (3). Further, the 1‐(2‐benzhydral‐4,6‐dimethylphenyl)‐3‐methyl‐4‐phenyl‐1H‐1,2,3‐traizol‐3‐ium iodide (4) was isolated from the reaction between 3 and methyl iodide. These molecules were examined by FT‐IR, TGA, CHN analysis, (1H and 13C) multinuclear NMR, UV–Vis, fluorescence, and SCXRD techniques. Molecules 2 and 3 depict the CH····π intermolecular interactions, while 4 exhibits a rare intermolecular I····HC(sp2) interactions (2.821 Å). The thermal stability of new super bulky triazole (3) and triazolium salt (4) was further exhibited by thermogravimetric analysis. The photophysical properties were investigated.