Raw materials with high levels of free fatty acids (FFA) are interesting alternatives to reduce costs in the biodiesel industry. Traditionally, these are processed by an esterification step followed by a transesterification stage. However, alternative processes can be economically more attractive, as the FFA separation from the oil, in order to carry out the reactions in separate. Among these, liquid-liquid extraction (LLEx) using an alcohol as the solvent and vacuum distillation can be applied. In this work, LLEx and distillation were compared regarding the FFA separation using process simulation in Aspen plus. A full factorial design was employed. For the extraction column, the parameters investigated were temperature, number of stages (N) and solvent/oil ratio, while pressure, N, feed stage and reflux ratio were considered for the distillation. The LLEx process proved to be technically more feasible than distillation one to keep the FFA content below 0.5% (wt) in oil rich-phase.