The chemosensor 3-phenyl-7-(pyrid-2-yl)-[1,2,3]triazolo[1,5-a]pyridine (PhPTP) used in combination with two different cyclodextrins, enable its solubilization and stabilization in aqueous solution. The behavior of the inclusion complex, and its binding ability in both cyclodextrins were investigated by means of absorption and fluorescence spectroscopy. The best results were obtained for PhPTP-DMβCD assembly, and its orientation in the DMβCD nano cavity was obtained by 2D-NMR. This inclusion geometry was confirmed by docking studies. The binary complex was proved as chemosensor upon the presence of different divalent cations in aqueous solutions. The PhPTP-DMβCD system, displays a high sensitivity for Fe(2+) by fluorescence quenching in neutral aqueous solution even in the presence of other metals showing high selectivity towards Fe(2+).