Supersonic beam of size-selected Ti-C6H6 metal-ligand binary complex was generated by a laser evaporation method followed by the size selection with 2-m long electrostatic hexapole field. The dependence of the beam intensity upon the hexapole field strength was measured in order to determine permanent dipole moment and complex symmetry. We find that the structure of Ti-C6H6 complex has nearly C-6v symmetry and its electric dipole moment is 2.4 +/- 0.3 D. The calculation with use of density functional theory substantiated its optimized structure as C-6v symmetric in accordance with the experimental result. The calculation also suggests that charge transfer interaction between Ti Atom and C6H6 plays a central role to stabilize the complex. (C) 2003 Elsevier Science B.V. All rights reserved.