A sterically encumbered isopropyl group substituted fluorescent triphenylbenzene based azo-linkedcovalent organic polymer, iPrTAPB-Azo-COP, has been synthesized by Cu(I) catalysed homo coupling (amineamine)reaction of 1,3,5-tris(4^'-amino-3^'

5^'-isopropylphenyl)benzene (iPrTAPB) under aerobic conditions. TheBrunauer-Emmett-Teller (BET) and Langmuir surface areas of iPrTAPB-Azo-COP have been estimated to be395 and 697 m² g^-1 with a pore diameter of 11.6 Å. Due to the presence of fluorescent triphenylbenzeneplatform iPrTAPB-Azo-COP exhibits broad emission band centred at 428 nm, when excited at 300 nm, as aresult of extended conjugation. The inherent fluorescent nature of iPrTAPB-Azo-COP has been utilized for sensing electron-deficient polynitroaromatic compounds (PNACs) such as a picric acid (PA), dinitrotoluene (DNT), p-dinitrobenzene (p-DNB) and m-dinitrobenzene (m-DNB). Further, iPrTAPB-Azo-COP has also been utilized for capture of carbon dioxide as the azo-COP is enriched with CO₂-philic nitrogen atoms apart from its microporosity. Since the azo (–N=N-) linkages are masked by the bulky isopropyl groups, iPrTAPB-Azo-COP exhibits a CO₂ uptake of 6.5 and 19.4 wt% at 1 bar and 30 bar, respectively, at 273 K.