The reaction of the bis(thiosemicarbazone) of dimethyl pyridine‐2,6‐diyl diketone, H2DAPTSC, with PbMe2(OAc)2, PbMePh(OAc)2 or PbPh2(OAc)2 in MeOH afforded the complexes [PbMe2(DAPTSC)], [PbMePh(DAPTSC)] or [PbPh2(DAPTSC)] (in the first two cases together with [Pb(DAPTSC)]). X‐ray crystallography of the Pb(IV) complexes showed that the metal has a pentagonal bipyramidal coordination sphere. The N3,S2‐bound DAPTSC2– anion occupied the equatorial plane and the organic groups were in the apical positions. These compounds retain the same coordination mode in DMSO solution. DAPTSC2– is also N3,S2‐bound in [Pb(DAPTSC)], a complex with a stereochemically active PbII lone pair. The reaction of PbPh2Cl2 with H2DAPTSC, also in methanol at room temperature, afforded [PbPh2(H2DAPTSC)]2[PbPh2Cl4]Cl2·6CH3OH. X‐ray crystallography of this centrosymmetric complex showed it to consist of two [PbPh2(H2DAPTSC)]2+ cations of similar structure to the neutral [PbR2(DAPTSC)] complexes, together with a trans‐octahedral [PbPh2Cl4]2– anion and two Cl– anions. This compound decomposes in DMSO solution, probably evolving to H2DAPTSC and PbPh2Cl2(DMSO)n. In order to evaluate the changes undergone by H2DAPTSC under metallation, the X‐ray structure of the free molecule was also determined.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)