A novel benzoxazine monomer (UPA) had been synthesized by the reaction of urushiol with formaldehyde and propylamine. From the ring-opening reaction of UPA, the corresponding new biobased resin polybenzoxazine (PUPA) was obtained. The PUPA was used to fabricate honeycomb-structured porous films using the breath figures technique. The obtained films were characterized by scanning electronic microscopy. The results showed that PUPA films were highly ordered porous films. Furthermore, the PUPA porous films possess excellent acid, alkali and organic solvent resistance properties.