The preparation of three metal (Ag(I) and Hg(II)) complexes based on bis‐carbene ligands and correlative three precursors H2Ln·(PF6)2 (n = 1–3) were reported. In each cationic moiety of complexes 1 and 2 and the monomer of complex 3, two Ag+ (or Hg2+) ions and two Ln (n = 1–3) formed one 36‐membered macrometallocycle. There existed π–π interactions between two naphthalenes in each cationic moiety of 1 and 2. The monomers of 3 were connected together through HgO bonds to form 1D chain. In the crystal packings of 1–3, two‐dimensional and three‐dimensional supramolecular structures were formed through CH˙˙˙π contacts and CH˙˙˙F H bonds. Additionally, the recognition capacity of 1 for H2PO4− was studied via fluorescence spectra, UV/Vis spectra, HRMS, 1H NMR titrations, and infrared (IR) spectra.