Employing Raman spectroscopy, we have studied the electronic structure of the charge-ordering system, Φ-(ET) 2 X, the dihedral angle (ψ) of which ranges from 100 to 121°. The most stable metal, Φ-(ET) 2 I 3 , (ψ = 100°) has a uniform charge distribution in a whole temperature range. The compounds with ψ > 111° have an inhomogeneous charge distribution even above the CO transition, which implies that the charges have localized nature in a whole temperature range. These localized charges are long-range ordered in the CO phase, whereas they are fluctuating randomly or forming short-range ordered domains above the CO phase transition. © Springer Science+Business Media, Inc. 2006.