The preparation of small focused libraries of supported catalysts and reagents represents an intermediate approach lying between combinatorial and single-compound methodologies. In this case, the potential structural variations can be selected according to previous studies in solution, to limit, to a reasonable extent, the number of components of the library. In our case, we have applied this strategy to the optimization of the structure of supported chiral amino alcohols for their use in catalytic processes (addition of ZnEt2 to benzaldehyde) as well as in noncatalytic reactions (lithium aluminum hydride reduction of acetophenone). This approach allows taking into consideration simultaneously both the structural variations on the chiral unit and the role of the support.