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Antifouling epoxy resin serves as a member of advanced nanocomposite coatings and engineered surfaces. Nevertheless, developing an antifouling epoxy composites is a state‐of‐the‐art technology. Herein, a complex nanostructure is tailored to be served as an advanced additive giving the antifouling characteristics to the epoxy resin. F‐POSS@HNT hybrid nanostructure, that is, halloysite nanotubes (HNTs) decorated with fluorinated polyhedral oligomericsil sesquioxane (F‐POSS), was synthesized and characterized. Chemical structure changes, thermal stability and morphology of hydroxylated HNTs (hHNTs) intermediate and F‐POSS@HNT ultimate nanostructures were analyzed by FTIR spectroscopy, TGA and TEM, respectively. The F‐POSS@HNTs catalyzed the epoxy‐amine crosslinking reaction, taking "Good" or "Excellent" crosslinking tags an quantified by the "Cure Index." The apparent activation energy values were calculated for the epoxy (reference), epoxy/hHNTs, and epoxy/F‐POSS@HNTs systems (26, 51, and 47 kJ mol−1, respectively). Contact angle measurements were performed via dynamic tests demonstrating improved hydro‐ and oleophobicity of the thermoset composites. The advancing contact angle with diiodomethane increased 36% and 30% for nanocomposites containing 5 and 10 wt.% of the developed hybrid nanostructure, respectively, compared with the neat epoxy. Likewise, 54% and 67% reduction in paraffin fouling in the same order confirmed their antifouling ability. Regarding self‐cleaning characteristics, 24% and 33% surface recovery were observed, respectively. Highlights: Antifouling surface was achieved in epoxy thermoset nanocomposites for potential industrial applications.Self‐cleaning behavior correlated with low wetting and antifouling properties.F‐POSS@HNT nanofillers were synthesized and successfully added to epoxy matrix.Both hHNT and F‐POSS@HNT showed a beneficial autocatalytic effect on epoxy‐amine reaction yielding satisfactory polymer crosslinking.Activation energy was reduced by incorporating F‐POSS@HNT compared with hHNT, signature of facilitated crosslinking. [ABSTRACT FROM AUTHOR]