Experimental results for the separation of triacylglycerols and free fatty acids mixtures by molecular distillation are reported. The experiments were carried out so as to evaluate the effect of relevant operating conditions on the performance of the separation. Mixtures with different compositions were distilled at pressures of 1 and 4 mbar, with temperatures ranging from 40 to 80 C, mass flows from 0.95 to 7.65 g/min, and wiper speeds from 0 to 400 rpm. Distillate and retentate products were weighed and evaporated fractions were calculated. The results were compared with those predicted by the use of the Langmuir Knudsen equation together with a functional group contribution method to estimate the vapor pressure of the components. The approach provided a good basis to model the experimental results for the separation by molecular distillation of binary mixtures of free fatty acids and triacylglycerols, as well as for mixtures of several free fatty acids.