The controlled synthesis of a series of polybenzoxazine model oligomers is described. A synthetic strategy is developed in which bromine is used as an ortho position blocking group allowing a stepwise synthesis of structurally uniform compounds. Debromination and subsequent hydrogenation is achieved in high yields by using activated Raney nickel catalyst in a methanol/aqueous base reaction medium. An effective hydrogenation procedure that does not require the addition of hydrogen gas is described. Polybenzoxazine oligomers as large as the model tetramer are synthesized. Applications for these strategies and procedures toward the synthesis of a variety of polybenzoxazine structures are described. Model oligomeric compounds of polybenzoxazines have been characterized by Fourier transform infrared spectroscopy (FT-IR), UV-visible spectroscopy, nuclear magnetic resonance spectroscopy (NMR), high performance liquid chromatography (HPLC), and size exclusion chromatography (SEC). Those oligomers used are the dimer, trimer, and tetramer of a monofunctional benzoxazine resin. Additional model compounds have also been synthesized. They are 2,6-bis(dimethylaminomethyl)-4-methylphenol and 2,6-bis(N-ethyl-N-methylaminomethyl)-4-methylphenol, which were used as model compounds to aid infrared band assignments.