Pool boiling heat transfer in water/glycerol binary solutions has been experimentally investigated on a horizontal rod heater. The experiments have been performed at various concentrations (zero to 35% mass glycerol) and heat fluxes up to 92 kW m2 at atmospheric pressure. The experimental values of boiling heat transfer coefficient have been compared to main existing correlations. It has been shown that the various predictions are significantly inconsistent. Based on the high difference between relative volatilities of water and glycerol, a simple model has been proposed to predict the boiling heat transfer coefficient. The applicability of this model is limited to low concentrations of glycerol and medium/low heat fluxes; however, the predictions are accurate. The proposed model is anticipated to be extendable to other binary systems in which the vapor pressure of one constituent is considerably higher when compared to the other component.