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The presence of water in coal presents a technological challenge for its industrial use in energetic processes. Water tends to negatively affect the coal quality and its net heating value (NHV), in addition to affecting its transportation costs. Therefore, this study aims to investigate the effects of glycerol and temperature on water adsorption onto systematically modified coals. A Colombian bituminous coal sample was used as support for being modified with glycerol. The virgin coal and modified coal were characterized by nitrogen adsorption at 77 K (SBET), scanning electron microscopy (SEM), Fourier transform infrared (FT-IR) spectroscopy, elemental analysis (C–H–N elemental), and thermogravimetric analysis (TGA). The results showed that the water uptake decreased as the amount of glycerol on the coal surface increased. The optimum concentration of 8 wt% of glycerol impregnated on the coal minimized water adsorption. Over a range of water activity evaluations, this amount of glycerol (C8) reduced water adsorption by approximately 60% compared with nonimpregnated coal (C0). As expected, water uptake decreased with increasing temperature. These results are reflected in the NHV with an increase of 17% for the C8 sample compared with the other samples evaluated. The Talu and Meunier model was used to fit the experimental adsorption isotherms, and the mean square root error (MSRE%) was lower than 10%. The isosteric heat of sorption (IHS) for coal tends to decrease as the amount of adsorbed water increases. In addition, the value of IHS decreases as the concentration of glycerol increases due to the blocking of polar adsorption sites present on the coal surface, which are the main regions of low uptake of adsorbed water. Additionally, the Gibbs free energy was found to have negative values, which corroborates the spontaneous adsorption process.