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Superhydrophobic technology in construction can effectively improve the barrier ability of the substrate to harmful water-based erosion media, among which the coating scheme is the most practical choice at present, but it may easily fail due to mechanical damage. Therefore, the current research focus has shifted to the development of internal superhydrophobic materials (ISMs) that maintain stable hydrophobicity even under harsh conditions of use and do not rely on expensive fluor-based surface modifications. In this study, the topological structure of waste denitrification fly ash (FA) was constructed using an innovative method, by precisely controlling the etching medium concentration and the form of FA, a one-step process was developed to create ISM with excellent matrix strength and strong waterproof properties. In this study, the alkaline environment generated by FA hydration was used to induce the silica-hydrogen bond dehydrogenation of polymethylhydrosiloxane (PMHS) and the free ammonium ion deamination to toughen the film; PMHS and liquid phase are used to produce the oil-water phase, and the oil film adheres to the surface of the generated NASH and sodium silicate crystals; The porous inner surface of ISM is formed with hydrogen- and ammonia-induced rough structure; The synthesized ISM retains superhydrophobicity and less compressive strength reduction value, and its superhydrophobicity even at damaged or friction interfaces. The material preparation method provides a good foundation and innovative design concept for the seepage prevention and maintenance of concrete structures, the construction of aerated FA bricks, the preparation of foam insulation materials, and the batch utilization of waste FA. • Denitrification fly ash is prepared into a masonry structure with internal hydrophobicity. • The mechanism of hydrophobic synergism between PMHS dehydrogenation film formation and fly ash etching deamination was revealed. • The internal and external wear resistance of the inner superhydrophobic material has been applied to actual engineering. [ABSTRACT FROM AUTHOR]