Herein, we have reported a tetraphenylethylene (TPE) based fluorescent chemosensor 4,4′,4′′,4′′′‐(ethene‐1,1,2,2‐tetrayl)tetrakis(N,N‐dimethylaniline) (TPE‐DMA) for the selective detection of explosive nitroaromatic compounds (NACs), such as 2, 4, 6‐trinitrophenol also called as picric acid (PA), 2,4‐dinitrophenol (DNP), and p‐nitrophenol (NP) over other NACs in CHCl3. TPE‐DMA is highly selective and sensitive toward PA in presence of various metal ions and anions. The quenching efficiency can be calculated from the Stern‐Volmer equation and was found to be 4.02×104 M−1, 1.82×104 M−1and 3.12×104 M−1 respectively for PA, DNP and NP. The detection limit of TPE‐DMA towards PA, DNP and NP of about 4.088×10−6 M, 5.155×10−6 M and 3.989×10−6 M respectively. Furthermore, to study the practical applicability of TPE‐DMA, visual‐eye detection was performed not only in solid‐state on TLC plates but also in solution state in CHCl3 under visible light as well as UV light illumination.