(Liquid + liquid) equilibrium for (N,N-dimethylformamide (DMF) + n-hexadecane) at temperatures from (293.15 to 313.15) K and for ternary mixtures of (DMF + hexadecane) with either quinoline, or pyridine, or pyrrole, or aniline, or indole at T = 298.15 K were determined at atmospheric pressure with stirred and thermoregulated cells. The NRTL and UNIQUAC models were used to correlate the experimental data. In addition, the extraction capability of DMF for heterocyclic nitrogen compounds was investigated with respect to distribution and selectivity.