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A novel derivative of aromatic polyethersulfone (PES) was obtained by bromination. Victrex PES was reacted with bromine under various conditions: in solution, in suspension, and without solvent; with or without catalyst; and at low and elevated temperatures. Practically no bromination occurred in solution; in the other cases, brominated PESs to various extents were obtained. The degree of substitution (DS) varied between 0.3 and 2.3. It was found that no catalyst is required for this reaction; the temperature, the concentrations of bromine and of polymer in the reaction mixture, and the duration of the reaction are the determinant factors of the DS. The modified polymers were characterized by elemental analysis, 1 H-NMR, 13 C-NMR, and PGC-MS, and their thermal properties were investigated by TGA and DSC methods. Further transformations of brominated PES as well as other new chemical reactions of PES will be the subject of later publications.