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[Display omitted] • A hexaazatriphenylene (HAT)-based sensor is designed and synthesized. • The sensor selectively recognizes Ag+ ion with excellent selectivity, reversibility and fast-response. • The advantages of the sensor enable it to be capable of serving as a new type of colorimetric and fluorescent chemosensor. Herein, by symmetrically merging six thiophene units into the hexaazatriphenylene (HAT) core, a HAT-based sensor (1) was designed and synthesized, which was found capable of exhibiting selective recognition of Ag+ with detection limit as low as 1.79 × 10−6 M in chloroform featuring with significant fluorescence "turn-off" property. Through the systematical investigation with UV–Vis absorption, fluorescence spectroscopy and the naked-eye experiments, as well as the 1H NMR titration and the Job's plot, it was revealed that sensor 1 could complex with Ag+ in a stoichiometric ratio of 2:3. We envisage the construction of such a thiophene-derived HAT molecule is conducive to exploring new type of Ag+ sensors, and it also will bring potential application in environmental detection. [ABSTRACT FROM AUTHOR]