The use of a diffuse reflectance IR spectroscopy technique as a tool for optimizing synthesis of 2-polystyrylsulfonamidoethanol, a new type of polymer support used in solid-phase organic synthesis was reported. Polystyrylsulfonylchloride resin was reacted with aminoethanol in the absence or presence of solvents and/or catalysts to give 2-polystyrylsulfonamidoethanol resin. The diffuse reflectance IR spectra were used to follow up the reaction process. It was found that the diffuse reflectance IR spectroscopy is a useful tool in optimizing preparation of new functional polymers. The optimal condition for preparation of 2-polystyrylsulfonamidoethanol is the reaction of polystyrylsufonylchloride with aminoethanol at 60C for 30 min.