ABSTRACTHydroxyalkyl derivatives of polyaminostyrene (PAS), polyallylamine (PAA), and polyethyleneimine (PEI) containing a 2,3‐dihydroxypropyl moiety with a high degree of modification were synthesized. The chemical structures of the polymer transformation products were characterized with elemental analysis, Fourier transform infrared spectroscopy, 1H‐NMR spectroscopy, and 13C‐NMR spectroscopy in the solid state. PAS reacted with glycidol and formed poly[N‐(2,3‐dihydroxypropyl)aminostyrene] with a high degree of functionalization. PAA revealed primarily the graft polymerization of glycidol. In the case of PEI, primary amino groups allowed the formation of an N‐derivative of 3‐aminopropanediol‐1,2. The PAA‐based sorbent showed a high sorption capacity toward boron ions in both acidic and alkaline media. From the sorption isotherm data, the maximum sorption capacity of this sorbent at pH 4 was determined to be 3 mmol/g. The PAS‐based resin maintained a high capacity between pH 9 and 12; the optimum pH was 12. The sorption capacity was 1.7 mmol/g. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43939.