High nuclearity [Mn10M2] clusters have been achieved through a self-assembly approach where multiple coordinating functional groups are incorporated into one ligand. When the hydrazone group appended with an oxime function as a reactive intermediate is used, the attachment of a vanillin subunit creates a ligand (L4) with three coordinating groups, which in their own right lead to cluster assemblies. The trifunctional ligand L4 produces a series of self-assembled, mixed oxidation state (Mn(II)/Mn(III)) Mn10M2 based clusters with an overall linear structure comprising two connected pentanuclear Mn-5 halves, which bind alkali metal cations (M = Li, Na, K, Rb, Cs) and H3O+ in the vanillin (O-6) end pockets, created by the assembly of three ligands around each Mn-5 subunit. Antiferromagnetic exchange dominates the spin coupling in the Mn-10 complexes, and surface studies on highly oriented pyrolytic graphite (HOPG) clearly show the arrangement of metal ions (Mn, Cs) in the Mn10Cs2 linear cluster assembly.