The stability of five different [Pd-n(N-donor)(m)](2n+) assemblies was examined by performing disassembly experiments with pyridine and with trifluoroacetic acid. Pyridine-induced disassembly was found to be most pronounced for Pd complexes containing N-donor ligands of low basicity. At the same time, these assemblies displayed high acid resistance. The contrasting stability in the presence of acid or pyridine can be used for the pH-controlled switching between different metallosupramolecular structures.