The present work is proposed to synthesize photosensitive benzoxazines using Schiff base (HNDT) with different amines like (aniline (a), 2-aminopyrimidine (ap), furfurylamine (ffa), 1-(−3-aminopropyl)imidazole (api), 3-aminopyrazole (apy), isoxazole-3-amine (ia)) and paraformaldehyde through Mannich condensation reaction. The structure of synthesized photosensitive benzoxazines was confirmed by using ATR-FTIR, 1H-NMR and 13C-NMR spectral techniques. The curing behavior of HNDT-a, HNDT-ap, HNDT-ffa, HNDT-api, HNDT-apy and HNDT-ia benzoxazine monomers was studied using differential scanning calorimetry (DSC). The thermal stability of polybenzoxazines was studied by thermogravimetric analyzer (TGA) technique. Among the synthesized polybenzoxazines poly(HNDT-ia) exhibited highest char yield value of 72% at 850°C. The limiting oxygen index (LOI) value of polybenzoxazine was calculated from residual char yield value and showed that all the polybenzoxazines exhibited self-extinguishing behavior. The hydrophobic nature of synthesized polybenzoxazine was studied by using contact angle goniometer and the values range from 124° to 136° which showed the hydrophobic nature. The antimicrobial activity of the synthesized benzoxazine monomers was studied by using S. aureus and E. coli a gram positive and a gram negative bacterium as the target bacteria. The photosensitivity nature of the synthesized monomers was studied using UV-Visible and fluorescence spectroscopic techniques. The results from optical studies showed that developed benzoxazines can be utilized for coating applications in addition to aggregation-induced emission (AIE) and dynamic light scattering characteristics.