The interaction between DNA and counter-ions of different valence, including sodium chloride (Na+), magnesium chloride (Mg2+), hexammine cobalt III ([Co(NH3)6]3+), and spermine ([C10N4H30]4+), is investigated by dynamic light scattering. It is found that the ratio of electrophoretic motilities of DNA in a buffer containing Na+ and Mg2+ is about 2:1, when the concentration of counter-ions c≥ 5 mM. But the ratio of DNA motilities in a buffer containing Na+ and [Co(NH3)6]3+ is about 4.5:1. When c<5 mM, the ratio grows with increasing concentration of counter-ions. DNA charge reversal can be observed in the case of quadrivalent counter-ion. The experimental results are in good agreement with the Manning counter-ions condensation theory for cases of monovalent or bivalent counter-ions. However, when the valency of counter-ions is equal to three, the experimental data deviates from the expectation of the theory significantly. For the quadrivalent counter-ions, the counter-ions condensation theory, which is based on the average field, fails. Furthermore, through the atomic force microscopy, it is found that DNA molecules will condense into compact structures when the valency of counter-ions is equal to or greater than three. Thus, the conformation of polyelectrolyte in free solution and the ion correlation play an important role in the migration process of polyelectrolyte.