This paper describes a novel strategy for the preparation of chemical microarrays using macro-molecular scaffolds. The macromolecular scaffolds are first functionalized with ketone groups and compounds of interest containing an aminooxy group are conjugated onto the ketone-modified scaffolds through a chemoselective oxime ligation. The conjugate mixtures are then spotted directly onto a plastic or glass surface to form compound microarrays. Because a constant amount of scaffold is used in the presence of excess compound in the ligation reaction, the amount of compound actually immobilized per microarray spot is constant and dependent on the scaffold concentration. Using this approach, 60 different peptides were ligated to human serum albumin or agarose scaffolds, and the peptide conjugates subsequently printed on glass or polystyrene surface to form microarrays. These peptide microarrays were subsequently evaluated and optimized for binding of Jurkat leukemic cancer cells.