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This work reports the experimental vapor-liquid equilibrium data of {ethanol(1) + glycerol(2)} and {tert-butanol(1) + glycerol(2)} systems. Boiling pressures were measured using a static synthetic method over the temperature range of 423–523 K. The experimental data were fitted using the Peng Robinson equation of state (PR-EoS) coupled to classical van der Waals mixing rules, quadratic regarding the composition. Results presented in this work may be relevant in process design of glycerol etherification.