The dielectric relaxation times τ and dipole moments μ of N-methylacetamide (NMA) mixed with N,N-dimethylformamide (DMF) in benzene solutions have been obtained using standard standing wave microwave techniques and Gopala Krishna’s single frequency (9.90 GHz) concentration variational method at 25, 30, 35, and 40 ◦C. The energy parameters (ΔHε , ΔFε , ΔSε ) for the dielectric relaxation process of mixtures with equal amounts of NMA and DMF have been calculated and compared with the corresponding energy parameters (ΔHη , ΔFη , ΔSη ) for the viscous flow. On the basis of the observations it is found that the dielectric relaxation process can be treated as a rate process like the viscous flow. Solute-solute and solute-solvent types of the molecular associations have been predicted