A new series of heterometallic tetranuclear complexes [Fe2Ln2(piv)6(thmp)2(MeOH)4]·solvent (Ln = DyIII (1); GdIII (2); TbIII (3); H2piv = pivalic acid) has been prepared from the reaction of -oxo trinuclear iron pivalate with Ln(NO3)3·nH2O and 1,1,1-tris(hydroxymethyl)propane (H3thmp) ligand in methanol solution. Single-crystal X-ray diffraction analysis reveals that complexes 1 and 3 crystallize in the monoclinic C2/c space group, and complex 2 in the monoclinic space group P21/c. The core of 1-3 is composed of two FeIII atoms and two LnIII atoms bridged by two thmp3- ligands and four pivalates (Figure). Two methanol and pivalate complete the coordination surrounding of two lanthanides. Each FeIII atom is six-coordinated and has an octahedral O6 geometry with two O atoms from two carboxylates and four O atoms from two thmp3- ligands. All Ln(III) atoms are nine-coordinated with an O9 environment through four O atoms of three carboxylate moieties, three O atoms from two thmp3- ligands and two O atoms from methanol molecules.