Induced circular dichroism has been used to study the binding of thionin molecule to twelve guanine-rich quadruplexes. Substituting the base in the loops and varying the length of the tails could substantial change the induced circular dichroism spectra, which allow us to distinguish structural isomers and to determine the binding sites of quadruplexes. Our results show that external stacking on the end surface of the G-quartet associated with electrostatic interaction with the loops or tails is the major binding mode of thionin with these G-quadruplexes.