Polybenzoxazine (PBZ), a novel class of high performance thermosetting phenolic resin, has been developed in order to overcome many shortcomings of conventional phenolic materials from either novolac or resole type resins. The paper first provides the overview of this high temperature material including main types, chemical structure of each type, and properties of the polymer, especially the synergistic behavior in thermal properties. It then describes the manufacturing technique to produce the monomeric resin as well as some applications of the polymer. (C) 2012 Elsevier Ltd. All rights reserved.