In this paper, the equation of state-Gibbs energy (EOS-G(E)) model was examined for the prediction of liquid-liquid equilibria (LLE) at high pressure on the basis of LLE data at 0.1 MPa. Four binary methanol + hydrocarbon systems were tested using the Peng-Robinson EOS (PR EOS), modified by Stryjek and Vera (PRSV), and the MHVI, MHV2, and Wong-Sandler (WS) mixing rules combined with two excess Gibbs energy models: the modified Wilson (T-K-Wilson) equation proposed by Tsuboka and Katayama, and the UNIQUAC equation. The adjustable parameters in the EOS-G(E) model were determined from our LLE data at 0.1 MPa.