The synthesis and application of polybenzoxazine adsorption resin was studied. First, the precursor was synthesized by the solventless method. And then a kind of spherical and granular polybenzoxazine resin was obtained using reverse-phase suspension polymerization technique in the process of solidification. Besides, the influence of dispersion medium, the volume ratio of precursor to medium, the solidification temperature, and the agitation speed were studied in detail in the process of polymerization. Second, the spherical shape of the polybenzoxazine resin was identified by scanning electronic microscope and the thermal stability of resin was measured by thermogravimetric analysis. Finally, the adsorption capacity of the spherical resin on pyridine was studied in cyclohexane systems. The correlation coefficient of Langmuir adsorption constant temperature line was bigger than 0.99, which indicated that the equilibrium sorption date was coincident with the Langmuir isotherm equation. And the saturated adsorptive capacity of dried resin achieved 222.2 mg g(-1). (c) 2007 Wiley Periodicals, Inc.