Two sets of tripodal ligands resulting from the reaction of 2-hydroxy-3-methoxybenzaldehyde (o-vanillin) with 1,1,1-tris(aminomethyl)ethane, Me–C(CH2NH2)3, or with N,N′,N″-trimethylphosphorothioic trihydrazide, P(S)[NMe–NH2]3, yield heterotrinuclear 3dII–4fIII–3dII complexes in which the 3d ions (MnII, FeII, CoII, NiII, and ZnII) occupy the inner N3O3 coordination sites while the 4f ions do assemble two of these 3d metal–ligand units. As the 3d coordination induces helicity, these achiral ligands can yield homochiral (Λ–Λ or Δ–Δ) or heterochiral (Λ–Δ) trinuclear heterometallic complexes, which mainly precipitate as racemates in centrosymmetric space groups. These two series of complexes differ in their preparation: those involving phosphorus atoms can be isolated in an open atmosphere, while the other series requires an inert atmosphere. Heterochiral (Λ–Δ) trinuclear complexes are only characterized with the ligand involving phosphorus atoms, while conglomerates are limited to the complexes, implying NiII 3d ions in this series. Conversely, a greater number of complexes that crystallize as chiral assemblies are isolated with the other ligand coordinated to the MnII, FeII, CoII, and ZnII ions and 4f ions ranging from DyIII to LuIII. This difference arises from the propensity of this ligand to favor the trigonal pyramidal geometry around the 3d ions. The synthetic strategy consisting in introducing a supplementary metal ion (here, a 4f ion) to a mixture of conformers (here, Λ and Δmononuclear 3d complexes) can yield homochiral complexes (here, Λ–Λ or Δ–Δtrinuclear molecules) that crystallize as racemates in centrosymmetric space groups and sometimes as chiral assemblies in noncentrosymmetric space groups. This approach provides a method for preparing chiral complexes with ligands that lack chiral atoms. Regarding the magnetic properties of the two series, we have first shown that they exhibit a similar magnetic behavior. It has also been previously demonstrated that the introduction of Gd ions suppresses quantum tunneling of magnetization in the absence of an applied field. Combining strongly anisotropic metal ions having a large angular momentum with a large isotropic metal ion, along with a ferromagnetic interaction in between these ions, appears to be an effective strategy for designing efficient single-molecule magnets.