Methods for producing ligand arrays, e.g., peptide 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 one embodiment of the subject methods, a substrate having a surface displaying acetate functional groups that produce surface bound hydroxyl functional groups upon hydrolysis is first provided, where the acetate groups are then hydrolyzed to hydroxyl functional groups. In another embodiment of the subject methods, a substrate having a surface displaying alkenyl functional groups is first provided, where the alkenyl functional groups are then converted to carboxylic functional groups. The resultant substrates, optionally after an additional functionalization step, are 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. The subject methods find use in the preparation of a variety of different types of arrays, where the produced arrays find use in a variety of different applications, including both genomic and proteomic applications.