Experimental liquid-liquid equilibrium (LLE) data were measured for benzene + cyclohexane + N,N-dimethylformamide (DMF) + potassium thiocyanate (KSCN) at atmospheric pressure and 303.15 K. The experimental data was correlated using the Othmer-Tobias correlation. The selectivity coefficients of DMF + KSCN for benzene are 2 to 11 in this work. The results revealed that the selectivity coefficients increased with the decrease in concentration of benzene in the raffinate and increased with the increase of the mass fraction of KSCN in the DMF + KSCN mixture. Considering the high selectivity for benzene, DMF + KSCN may be used as a potential extracting solvent for the separation of benzene and cyclohexane.