Structural characteristics and thermodynamic properties of dG(3)(T(2)AG(3))(3), d(C(3)TA(2))(3)C-3 and dG(3)(T(2)AG(3))(3)/d(C(3)TA(2))(3)C-3 were intensively investigated. It was indicated that metal ions greatly affected the conformation and stability of the G-quadruplex. A competition of a structure transition among the G-quadruplex, I-motif, and the duplex was confirmed to be dependent on both cation species and pH values. The structural competitive mechanism is discussed for the first time. This study shows an intriguing potential in modulating DNA structures in vivo, which is of great importance in drug design and cancer chemotherapy. (C) 2002 Federation of European Biochemical Societies. Published by Elsevier Science B.V. All rights reserved.