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A known trinuclear structure was used to design the heterobimetallic mixed‐valent, mixed‐ligand molecule [CoII(hfac)3−Na−CoIII(acac)3] (1). This was used as a template structure to develop heterotrimetallic molecules [CoII(hfac)3−Na−FeIII(acac)3] (2) and [NiII(hfac)3−Na−CoIII(acac)3] (3) via isovalent site‐specific substitution at either of the cobalt positions. Diffraction methods, synchrotron resonant diffraction, and multiple‐wavelength anomalous diffraction were applied beyond simple structural investigation to provide an unambiguous assignment of the positions and oxidation states for the periodic table neighbors in the heterometallic assemblies. Molecules of 2 and 3 are true heterotrimetallic rather than a statistical mixture of two heterobimetallic counterparts. Trinuclear platform 1 exhibits flexibility in accommodating a variety of di‐ and trivalent metals, which can be further utilized in the design of molecular precursors for the NaMM′O4 functional oxide materials. [ABSTRACT FROM AUTHOR]