Novolac resin was modified with 3-aminopropyltrimthoxysilane to obtain phenol-formaldehyde-aminopropylsiloxane resin (PF-APS). Fourier transformation infra-red spectra, thermogravimetric analysis, elemental analysis, and pH-metric titration were used to characterize PF-APS. Its chemical formula was suggested to be C14H12.49N0.1O2Si0.1. The resin shows high experimental metal ions uptake capacity within short time of equilibration. The metal capacity was determined by atomic absorption spectrometry to be 0.787 mEq Cu/g. Maximum separation efficiencies of Cu2+, Cr3+, and Ni2+ from aqueous solutions on PF-APS were at pH 8.0 and time of stirring 60 min; 94.0%, 90.8%, 83.2%, respectively. No significant interference from the background ions Na+, Cl−, and was observed on the separation process. The heavy metal ions were eluted using 0.01 mol L−1 EDTA at 65°C releasing >94% of the separated metal ions. The method of separation was applied successfully to remove the heavy metal ions Cu2+, Cr3+, and Ni2+ from electroplating wastewater from Dekirnis, Dakahlia Governorate, Egypt. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40993.