The B-ala/AIBN PBZ system has a high extent of ring-opening of oxazine because phenol-containing oligomers are formed at the early stage of the curing process. As a result, the B-ala/AIBN PBZ system possesses a relatively stronger intramolecular hydrogen bonding and lower surface energy than the pure B-ala system at low temperature curing. In this context, poly(4-vinyl pyridine), poly(4-vinyl phenol) thin films and polycarbonate substrates, which lack liquid resistance, possess low surface free energy after modification with B-ala/AIBN = 5/1 PBZ.