The physicochemical modification of the filler allows changing the hydrophilic–hydrophobic properties and effectively influencing the processes occurring at the filler–binder interface, on which the physicomechanical characteristics of composites largely depend. The paper presents studies related to the modification of limestone-based filler effect on the degree of its hydrophobicity and wetting with liquids of different polarity, establishing the relationship between the characteristics of hydrophobized mineral powders and the adsorption capacity in relation to water. Using mechanochemical processing with hydrophobic components GF-1 and GF-2, it was possible to obtain fillers with a sufficiently high content of hydrophobic particles (58.2% and 85.9%, respectively). It was found that the results of the contact angle (123.6° and 114.5°, respectively) and the degree of hydrophobicity do not quite correlate with each other. It was noticed that the contact angle on the powder modified with GF-1 decreases with time. Studies of the powders’ thermal effects wetting of different polarity liquids via microcalorimetry allows us to establish that with an increase in the filler hydrophobicity degree, the integral heat of immersion decreases due to a significant decrease in the probability of chemical interactions between water and powder due to the adsorption of applied surfactants molecules on the limestone active centers. The revealed endothermic effects indicate the occurrence of physical interactions due to non-polar dispersion forces. Differences in the nature of heat release and heat absorption in modified fillers indicate significant differences in the composition and mechanism of action of the used surfactants, which affected the efficiency of hydrophobization. At the same time, a linear dependence of the moisture absorption and moisture indicators, determined by independent experiments, on the degree of hydrophobicity was established.