A series of new heterometallic compounds have been obtained by the co-crystallization of Cu(II) methoxy-substituted β-diketonates and Pb(II) hexafluoroacetylacetonate (hfac) from organic solvents. Their crystal structures were established by X-ray analysis. It is shown that the formation of heterometallic compounds proceeds with geometrical isomerization of the initial copper complexes, which can be controlled by varying terminal substituents in the ligand. Due to the ability of copper complexes to isomerize, the structure of the resulting heterocomplexes can be flexibly and purposefully changed from polymeric to discrete molecular forms. The study of the thermal properties shows that all the reported compounds are volatile and can be re-sublimed in a vacuum, with their composition and structure being retained.