Azeotropic mixtures can occur in alcohol and alkane systems because of their close boiling points and highly nonideal molecular force interactions, leading to vapor liquid coexistence envelopes with a maximum pressure. For this reason, it could be interesting from an academic and industrial viewpoint to find the appropriate solvents for separation processes involving azeotropic mixtures. Protic ionic liquids (PILs) are presented as an interesting alternative. This work reports liquid liquid equilibrium data for ternary systems of alkanes (n-pentane, n-hexane, n-heptane, or n-octane) + alcohol (methanol or ethanol) + PIL 2-hydroxyethanolamine formate (2-HEAF) at 298.15 K and atmospheric pressure (101.3 kPa). Distribution coefficient (D) and selectivity parameter (S) data were used to evaluate the extracting potential of ionic liquids in separating alcohol from alkanes. Tie-line data were correlated with the nonrandom two liquid (NRTL) activity coefficient model, presenting a mean global deviation error of 0.9818%.