In the present work, silica and titania reinforced polybenzoxazine (PBZ–SiO2–TiO2) hybrid nanomaterial possessing high surface free energy have been developed using dimethylol-functional benzoxazine monomer (4HBA-BZ), tetraethoxysilane (TEOS), 3-(isocyanatopropyl)triethoxysilane (ICPTS), titaniumisopropoxide (TIPO) through an in situ sol–gel process. Data obtained from the contact angle measurement indicate that the hybrid materials are hydrophilic in nature and possess a high surface free energy. For example, hybrid PBZ obtained from 1:1:0.6:0.4 (m:m:w:w) ratio of 4HBA-BZ:ICPTS:TEOS:TIPO (PBST4) exhibit a high surface free energy of 38.2 mJm−2 which is higher than that of neat polybenzoxazine (29.5 mJm−2). Further data resulted from thermal studies indicate that the hybrid PBZ possess higher values of Tg, thermal stability and char yield than those of neat PBZ.