New trifunctional polybenzoxazines were developed and utilized as a high‐potent coating material for superhydrophobic cotton fabrics and mild steel corrosion protection applications. New trifunctional benzoxazines resin have been synthesized using trihydroxytriphenylmethane (TTM) with dimethylaminopropylamine (dmapa), 1‐(3‐aminopropyl)imidazole (ipa) and aminoethoxyethanol (aee) as amine sources with paraformaldehyde through Mannich condensation. The structural confirmation of synthesized benzoxazines was ascertained by spectral studies. The ring opening polymerization of TTM‐Bzs was studied using DSC analysis. All the three TTM‐Bz monomers show curing temperature lower than 210°C. The thermo‐stability and water contact angle (WCA) of polybenzoxazines were studied using thermogravimetric analysis and goniometer, respectively. Among the TTM‐PBz studied, the poly(dmapa) exhibit better thermo‐stability and hydrophobic behavior when compared to rest of the synthesized polybenzoxazines. Poly(TTM‐dmapa)‐coated cotton fabric exhibits the superhydrophobic behavior and mild steel (MS)‐coated specimen possesses the higher charge transfer resistance value of 3.47 × 10 7 Ω cm 2 . It was also inferred that all the TTM‐PBz‐coated MS specimens exhibit higher corrosion protection behavior as well as good thermo‐stability and hydrophobic nature. Further, the obtained results suggested that these materials can be suitably exploited for hydrophobic anticorrosion applications with improved performance and enhanced longevity.