Methods of producing ligand arrays, e.g., polypeptide and nucleic acid arrays, as well as the arrays produced thereby, methods for use of the arrays and kits that include the same, are provided. In the subject methods, a substrate having a surface displaying carboxylic ester functional groups that produce surface bound hydroxyl functional groups upon hydrolysis is first provided. Next, the functional groups are hydrolyzed to hydroxyl functional groups. The resultant substrate, optionally after an additional functionalization step, is then contacted with ligands, e.g., via deposition of each different ligand onto a different region of the surface, resulting in covalent attachment of the contacted ligands to the surface.