Heterometallic single-source precursors for the Pb/Fe = 1:1 oxide materials, PbFe(beta-dik)(4) (beta-dik = hexafluoroacetylacetonate (hfac, 1), acetylacetonate (acac, 2), and trifluoroacetylacetonate (tfac, 4)), have been isolated by three different solid-state synthetic methods. The crystal structures of heterometallic diketonates 1, 2, and 4 were found to contain polymeric chains built on alternating [Fe(beta-dik)(2)] and [Pb(beta-dik)(2)] units that are held together by bridging M-O interactions. Heterometallic precursors are highly volatile, but soluble only in coordinating solvents, in which they dissociate into solvated homometallic fragments. In order to design the heterometallic precursor with a proper metal/metal ratio and with a discrete molecular structure, we used a combination of two different diketonate ligands. Heteroleptic complex Pb2Fe2(hfac)(6)(acac)(2) (5) has been obtained by optimized stoichiometric reaction of an addition of homo-Fe(acac)(2) to heterometallic Pb2Fe(hfac)(6) (3) diketonate that can be run in solution on a high scale. The combination of two ligands with electron-withdrawing and electron-donating groups allows changing the connectivity pattern within the heterometallic assembly and yields the precursor with a discrete tetranuclear structure. In accord with its molecular structure, heteroleptic complex 5 is soluble even in noncoordinating solvents and was found to retain its heterometallic structure in solution. Thermal decomposition of heterometallic precursors in air at 750 degrees C resulted in the target Pb2Fe2O5 oxide, a prospective multiferroic material. Prolonging the annealing time or increasing the decomposition temperature leads to another phase-pure lead-iron oxide PbFe12O19 that is a representative of the important family of magnetic hexaferrites.