Abstract The ethanol-water separation is very important because ethanol is widely applied in the chemical industry and its use as a fuel can reduce the pollution emitted to the air. However, anhydrous ethanol production using conventional distillation is impossible, at atmospheric pressure, due to the presence of an azeotrope. In the present work, experimental tests were carried out in order to evaluate the use of glycerol as an entrainer, in substitution of ethylene glycol in an extractive distillation. The use of glycerol is motivated by the biodiesel production units, due to the fact that it is the main byproduct and a new market is necessary to consume its overproduction. The experiments were carried out in a distillation column packed with Raschig rings, varying the glycerol/feed (ethanol and water) ratio, S/F, from 0.5 to 0.9. The samples were analyzed using a digital densimeter. The results showed that glycerol was effective to promote ethanol dehydration and the presence of an azeotrope was not observed using a solvent to feed ratio (S/F) equal to 0.9. Some empirical correlations were investigated to evaluate the HETP (Height Equivalent to a Theoretical Plate), and the results provided a useful tool for designing a packed bed column for ethanol-water separation.