A general methodology has been evaluated for the preparation and optimization and fine-tuning of polymer-supported chiral catalysts for the ZnEt 2 addition to benzaldehyde. This approach involves the use of parallel solid-phase chemistry and the use of cheap and easily available chiral starting materials, such as amino acids. In this way, small, focused polymer-supported libraries of α,α-substituted amino alcohols have been prepared and evaluated as chiral ligands for the above-mentioned catalytic reaction. This strategy allows for an easy and fast way to analyze the different factors affecting the efficiency of the supported species (including the polymeric network itself) and to improve the tuning of the chiral catalysts. For the cases studied, amino alcohols containing aliphatic α-substituents have been shown to give good results when in conjunction with both aliphatic side chains at the β position and a N-methyl substituent.