Infrared and Raman studies of sodium chlorate in N,N-dimethylformamide (DMF) at different concentrations allowed to observe changes that are interpreted in terms of the contact ion pair formation. As the DMF is an ionising solvent it was possible to observe the equilibrium between associated and non-associated chlorate. In addition, depolarisation measurements were used to distinguish between the asymmetric and symmetric band representations in almost all regions of this anion. The vibrational assignment is entirely satisfactory indicating that in the Na + ClO 3 - contact ion pair the local symmetry around ClO 3 - changes from C 3 v to C S . In addition, our results do not show any evidence for the formation of solvent separated ion pairs and aggregates in this system.