Paving the way towards new functional materials relies increasingly on the challenging task of forming organic–inorganic hybrid compounds. In that regard, discrete atomically-precise metal-oxo nanoclusters have received increasing attention due to the wide range of organic moieties that can be grafted onto them through functionalization reactions. The Lindqvist hexavanadate family of clusters, such as [V₆O₁₃{(OCH₂)₃C-R}₂]²⁻ (V₆-R), is particularly interesting due to the magnetic, redox, and catalytic properties of these clusters. However, compared to other metal-oxo cluster types, V₆-R clusters have been less extensively explored, which is mainly due to poorly understood synthetic challenges and the limited number of viable post-functionalization strategies. In this work, we present an in-depth investigation of the factors that influence the formation of hybrid hexavanadates (V₆-R HPOMs) and leverage this knowledge to develop [V₆O₁₃{(OCH₂)₃CNHCOCH₂Cl}₂]²⁻ (V₆-Cl) as a new and tunable platform for the facile formation of discrete hybrid structures based on metal-oxo clusters in relatively high yields. Moreover, we showcase the versatility of the V₆-Cl platform through its post-functionalization via nucleophilic substitution with various carboxylic acids of differing complexity and with functionalities that are relevant in multiple disciplines, such as supramolecular chemistry and biochemistry. Hence, V₆-Cl was shown to be a straightforward and versatile starting point for the formation of functional supramolecular structures or other hybrid materials, thereby enabling their exploration in various fields.