Polymeric microspheres with N-methyl-D-glucamine (NMDG) ligands have been tested in the adsorption-membrane filtration process for boron removal from aqueous solutions. The chelating resins were synthesized by reacting NMDG with the vinylbenzyl chloride-styrene-1,4-divinylbenzene (VBC/S/DVB) copolymer at the reflux temperature and in the microwave reactor. VBC/S/DVB spheres with a gel structure that contained 6 wt% DVB were obtained by membrane emulsification followed by suspension polymerization. By selecting the optimal emulsification and polymerization parameters, it was possible to obtain 25-microm-diameter particles with a narrow size distribution. Resins obtained by microwave modification showed the higher boron adsorption capacity.