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The paper evaluates the effectiveness of surface hydrophobization of high performance concrete (HPC) containing boiler slag (BS) and coal combustion dust (CCD). The following tests were performed: density, porosity, absorptivity, capability to diffuse water vapor, compressive strength, flexural strength, frost resistance, contact angle. The Wu method was used for the determination of surface free energy (SFE). The conducted studies showed that surface hydrophobization reduced the water absorption by weight and the capability to diffuse water vapor. Fourteen days after the test, a 69.9% drop in the absorptivity of the concrete containing 10% of BS was observed, in addition to 67% reduction in water vapor diffusion. Hydrophobization decreased the SFE in concrete with 5% boiler slag addition by a factor of 4, increased the contact angle as well as contributed to a 12-fold drop in mass loss following a frost resistance test, in the concretes with 10% BS addition.