Two series of photosensitive diarylidene cycloalkanones-based benzoxazines were synthesized using vanillylamine (va), tyramine (ty) and aminophenol (ap) with bis-hydroxyl derivative of divanillidene cyclopentanone (DVCP) / cyclohexanone (DVCH) through Mannich condensation. The structure of the synthesized benzoxazines were confirmed from ATR-FTIR and 1H-NMR spectral analyses. Curing behavior and thermal stability were studied using DSC and TGA, respectively. DVCP-ap/DVCH-ap-based benzoxazines exhibited the lowest curing temperature of 211 °C and 202 °C, respectively, than rest of the benzoxazines. Among the synthesized polybenzoxazines DVCP-ap/DVCH-ap exhibited higher char yield value of 55% and 57%. The α, β-unsaturated moiety present in the divanillidene cyclopentanone/cyclohexanone undergone 2π + 2π cycloaddition reaction to form cyclobutane on irradiation under UV light of 365 nm and leads to form a cross-linked network structure. Also, aggregation-induced emission has been explored by adding water fractions to the benzoxazine solvent mixture. Poly(DVCP-ty) exhibited the highest water contact angle value of 146° and possess an excellent corrosion protection efficiency of above 98% toward mild steel surfaces.