Synthesis, characterization, and properties of new thermally curable polysulfone containing benzoxazine moieties in the side chain were investigated. First, chloromethylation and subsequent azidation processes were performed to form polysulfone containing pendant clickable azide groups. Independently, antagonist 3,4-dihydro-3-(prop-2-ynyl)-2H-benzoxazine was prepared by using paraformaldehyde, phenol and propargylamine. The following copper(I) catalyzed azide-alkyne cycloaddition click reaction was applied to obtain self-curable polysulfone with pendant benzoxazine units. The polymer and intermediates at various stages were characterized by 1H-NMR, 13C-NMR and FT-IR spectroscopies. The thermal properties and curing behavior of final polymer were investigated by differential scanning calorimetry and thermal gravimetric analysis. Compared to the neat polysulfone, the obtained polymers exhibited thermally more stable polymers.