3‐Amino‐5‐(thiazol‐2‐yl)‐[1,1′‐biaryl]‐2,4‐dicarbonitriles have been synthesized employing a facile one‐pot pseudo four‐component domino strategy. All these thiazole‐tethered biaryls exhibited blue fluorescence under UV lamp. Based on the high relative quantum yield, three compounds namely, 4a, 4d, and 4i, were chosen to explore the metal interference studies. Against several metal ions, these three thiazole‐tethered biphenyl probes were found to be effective fluorescent chemosensors for the selective and sensitive detection of Fe3+ ions with a lower detection limit of 0.18, 0.12, and 0.16 μM, respectively.