The present work investigate the coating behaviors of a series of polybenzoxazines (PBZs) derived from N-phenyl pyrazolidine scaffold based bisphenol (PPBP) and long chain aliphatic amines. Initially, the prepared PPBP was verified for its non-toxicity in comparison with bisphenol-A. Subsequently, the PBZs prepared from PPBP displayed enhanced values of water contact angle (WCA) when coated over different substrates namely cotton fabric and mild steel. In specific, the poly(PPBP-dda) and poly(PPBP-oda) coated cotton fabrics delivered outstanding WCA values of 154.2° and 153.5°, respectively. Observations from SEM images suggest that poly(PPBP-dda), and poly(PPBP-oda) exhibit closely packed molecular arrangement contributing for rough surfaces due to presence of their long dodecyl(C12) and octadecyl(C18) chains, respectively. Subsequently the oil-water separation investigation using the poly(PPBP-dda) coated fabric delivered superior separation efficiency (98 %) and flux values [6330 L/(m2h)]. At the same time, the mild steel specimens when coated with poly(PPBP-dda) was also found to be less aggressive towards corrosion in artificial sea-water showing 81% efficiency and charge transfer resistance (Rct) of 280 Ω cm–2. Further, screening of the PPBP monomer and corresponding polybenzoxazines exhibited good antibacterial activity. Thus, a new type of PPBP based PBZs prepared in present work can lead further development of various new non-toxic substrates to replace bis-phenol derivatives.