This study focuses on methylol functional benzoxazines as precursors to build a network structure utilizing both benzoxazine and resole chemistry. The first part is a review of systems that contain methylol groups which play a role on their crosslinking formation. The polymerization mechanism and properties of resoles will be highlighted as the most abundant polymers that are characterized by polymerization through condensation reaction of methylol group. In the second part, the effect of incorporating methylol group into benzoxazine monomers is studied. Differential scanning calorimetry (DSC) is used to study the effect of methylol group on the rate of polymerization. Kissinger and Ozawa methods using non-isothermal DSC at different heating rates show that methylol monomer exhibits lower average activation energy compared to the un-functionalized monomer. The effect of adding catalysts into the monomers is also studied. p-Toluene sulfonic acid (PTSA) is found to be more efficient than 1-methyl-imidazole (IMD) and lithium iodide (LiI) in the case of methylol monomer due to its ability of accelerating both the methylol condensation and ring-opening polymerization. Additionally, thermal behavior of the monomers is studied using thermogravimetric analysis (TGA). (C) 2012 Elsevier Ltd. All rights reserved.