The isolation and full characterization of multinuclear Schiff base complexes is reported, and their relevance as precursors for octanuclear Zn(8) salen cluster complex formation is discussed. Starting from simple precursors, three tetranuclear Zn(4) complexes were accessed that incorporate typical half-salen units and comprise of bridging acetates. The use of alternative reaction conditions or a step-wise approach smoothly leads to Zn(8) cluster formation. In addition, the tetranuclear Zn(4) complexes themselves may also serve as precursors toward Zn(8) cluster formation when treated under appropriate reaction conditions. The influence of the solvent medium in the latter Zn(4) → Zn(8) conversion was separately studied and revealed the formation of unusual pyridine-ligated multinuclear structures with fully condensed salen coordination pockets, providing a possible prelude to octanuclear cluster formation.