Polybenzoxazine is a newly developed addition polymerized phenolic system, having a wide range of interesting features and the capability to overcome several shortcomings of conventional novolac and resole type phenolic resins. They exhibit (i) near zero volumetric change upon curing, (ii) low water absorption, (iii) for some polybenzoxazines T_g much higher than cure temperature, (iv) high char yield, (v) no strong acid catalysts required for curing, (vi) release of no byproduct during curing and also possess thermal and flame retarding properties of phenolics along with the mechanical performance. Though benzoxazine based materials possess several advantages, they have not yet became very attractive to the industries. To improve the mechanical properties and processibility several strategies have been reported including (i) synthesis of benzoxazine monomers with additional functionality, (ii) incorporation of benzoxazine in polymer chain, and (iii) benzoxazine based composites or alloys. In this article, we have discussed about the recent development of benzoxazine chemistry. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5565–5576, 2009