Two novel ferrocene-containing macrocyclic triazoles (L1 and L2) and their acyclic analogs (L3 and L4) were easily prepared by “click” reaction. The anions binding abilities of L1–L4 were evaluated by cyclic voltammetry and differential pulse voltammetry methods. The results revealed that the receptors L1–L4 have exclusive electrochemical sensing of H2PO4−, with the shift in redox potentials of L1–L4 towards the cathodic values. The binding mechanisms between the receptors and H2PO4− were examined by 1H NMR titrations and density functional theory (DFT) calculations.