A new and convenient protocol is presented for creating thick Emeraldine Green layers on crosslinked PS-DVB microspheres. This was performed by persulfate oxidation of anilinium salt of sulfonated linear poly (styrene) brushes tethered to the cross-linked poly (styrene-divinyl benzene) (PS-DVB) micro spheres. The carrier polymer was prepared by surface initiated ATRP of styrene from PS-DVB micro beads (210-420 mu m) and followed sulfonation by Vink process. Sulfonic acid groups (4.2 and 4.8 mmolg(-1)) on the surface brushes were then neutralized with aniline. Oxidation of the anilinium salts so formed on the microspheres proceeded solely on the polymer microbeads to give thick PANI layers. The red-brown Pernigraline generated by further oxidation of the PANI layer was demonstrated to act as an efficient Michael acceptor in covalent immobilization of amines, amino acids and polyamines in good to excellent yields (i.e. 1.7 mmolg(-1)) as inferred from FT-IR spectra and wet chemical analyses. (C) 2015 Published by Elsevier B.V.