Bis-benzimidazolium salt (S)-2,2′-bis[2″-(N-Et-benzimidazoliumyl)ethoxy]-1,1′-binaphthyl hexafluorophosphate [(S)-L1H2]·(PF6)2 and bis-imidazolium salts (S)-2,2′-bis[2″-(N-R-imidazoliumyl)ethoxy]-1,1′-binaphthyl hexafluorophosphate [(S)-L2H2]·(PF6)2 and [(S)-L3H2]·(PF6)2 (R = ethyl or benzyl), as well as their five N-heterocyclic carbene Hg(II) and Ag(I) complexes such as [(S)-L1Hg(HgBr4)] (1), [(S)-L2Hg(HgBr4)] (2), [(S)-L2Hg(HgI4)] (3), {[(S)-L2Ag](PF6)}n (4) and [(S)-L3Ag](PF6) (5) have been prepared and characterized. Each of complexes 1–3 consists of two rings (one 6-membered ring and one 11-membered ring), in which the oxygen atom in the ligand participates in coordination with Hg(II) ion. In complex 4, 1D helical polymeric chain is formed via biscarbene ligand (S)-L2 and Ag(I) ion. A 15-membered macrometallocycle is constructed through a ligand (S)-L3 and a Ag(I) ion in complex 5. Additionally, the selective recognition of H2PO4
− using complex 5 as a receptor was investigated on the basis of fluorescence and UV/vis spectroscopic titrations. The results indicate that complex 5 can distinguish effectively H2PO4
− from other anions.