A 2-haloimidazole-tetraphenylethylene ion-pair receptor 1 is shown to recognise only HSO4- anions in the presence of a cobound Zn2+ cation guest species, which induced a remarkable increase with concomitant blue shift of the emission band of the complex [1·2Zn]4+ whereas no affinity of the free receptor 1 by the anions is observed. In addition, the downfield shifts observed by 1H NMR of the Ha, Hb and Hc protons of the complex [1·2Zn]4+ upon the addition of HSO4- anions indicate their participation in the recognition event. According to DFT studies, upon chelating a Zn2+ cation with two imidazole nitrogen atoms, receptor 1 adopts a conformation ideally fitted to recognise HSO4- through a combination of C(sp2)-HO and C(sp3)-HO hydrogen bondings, C+(sp2)-BrO halogen bonding and C(sp2)O tetrel bonding.