gamma-Valerolactone is a biomass-derived compound widely applicable in chemical industry, especially as a solvent, additive to fuels, or precursor for other chemicals. In contrast with the industrial importance of gamma valerolactone, there is an insufficient number of mixture phase-equilibria in the literature. Therefore, the aim of this work was to measure liquid-liquid equilibrium data for ternary systems gamma-valerolactone + toluene + hydrocarbon (hydrocarbons were n-heptane, n-decane, n-dodecane, and cyclohexane) by the direct analytical method at 298.15 K and 0.1 MPa. The obtained experimental data were processed and correlated by the nonrandom two-liquid (NRTL) model. The NRTL binary parameters between gamma-valerolactone and toluene were evaluated from the measured ternary liquid-liquid equilibrium data, whereas the other binary parameters were obtained by regression of binary liquid-liquid equilibrium data or vapor-liquid equilibrium and excess enthalpy data taken from literature. The predictive performance of the perturbed-chain induced-polar SAFT (PCIP-SAFT) equation of state was also studied for the ternary systems. On the basis of the pure-components data only, the PCIP-SAFT predictions can be considered as relatively successful because of the ability of PCIP-SAFT to take into account the dipolar interactions.