Single crystals of alkoxy-functionalized hydroxamate/zinc metal-organic frameworks (MOFs) were obtained by fixating the hydroxamate moiety via intramolecular hydrogen bonding. The resulting MOF structures depend on the steric demand of the alkoxy groups, whereby the incorporation of bulky isopropyl groups affords porous hydroxamate/zinc MOFs. The topological structures of the isopropyl-substituted MOFs could be controlled by adding acid.