A one-pot strategy exploiting the structure directing effects of Se^IV and Te^IV heteroatoms has yielded the highest nuclearity noble metal containing polyoxometalates to date; including the palladium-rich selenotungstate isomers K₂₈[H₁₂Pd₁₀Se₁₀W₅₂O₂₀₆]·65H₂O (1) and K₂₆[H₁₄Pd₁₀Se₁₀W₅₂O₂₀₆]·68H₂O (2), and the nanoscale tellurotungstate cluster Na₄₀[Pd₆Te₁₉W₄₂O₁₉₀]·76H₂O (3). These reaction systems exhibit remarkable structural flexibility and point to a new route towards the synthesis of complex heterometallic species, in which multiple lacunary polyoxometalate ‘building blocks’ have been assembled to trap a transient oxopalladate species suspected to play a role in the assembly of several common polyoxopalladates. Mass spectrometry has been applied to explore and compare the solution stability of compounds 1–3, demonstrating the markedly different properties of the Se^IV and Te^IV templated systems. Electrochemical analysis of 1 has been provided and is dominated by Pd redox processes, with reduction of the cluster resulting in electrodeposition of Pd metal and observation of the subsequent formation of PdO species, concurrent with previously reported oxopalladate containing species.