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Three gallyl lanthanide complexes [{(dipp-Bian)Ga}2Ln(thf)4] (Ln = Sm, Eu, Yb; dipp-Bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene), in which the lanthanide atoms are coordinated by only two {(dipp-Bian)Ga}− ligands and THF, are reported. Two unsupported Ln–Ga bonds are found in each compound. The gallyl lanthanide complexes have been obtained by two synthetic pathways: (1) reductive insertion of the lanthanide metals into the Ga–Ga bond of [{(dipp-Bian)Ga}]2 and (2) salt metathesis of [(dipp-Bian)GaK(thf)5] with LnI2. Moreover, the samarium compound [{(dipp-Bian)Ga}2Sm(thf)4] was additionally obtained in a reductive pathway from SmI3 and [(dipp-Bian)GaK(thf)5]. The length of the Ln–Ga bond strongly depends on packing effects. The reaction of TmI2(thf)5 and [(dipp-Bian)GaK(thf)5] gave the Tm(III) complex [{(dipp-Bian)Ga–Ga(dipp-Bian)}(C4H8O)TmI(thf)5], in which one THF ring was opened and reduced twice, forming the formal double negative charged anion (O-CH2-CH2-CH2-CH2)2–. This thulium compound and its dysprosium analogue [{(dipp-Bian)Ga–Ga(dipp-Bian)}(C4H8O)DyI(thf)5] were also obtained in an alternative approach by reacting LnI2(thf)x (Ln = Tm, Dy) with [(dipp-Bian)Ga]2 in THF. All new compounds were structurally characterized by single-crystal X-ray diffraction. The ytterbium complex shows the shortest Yb(II)–Ga bond distances reported so far. [ABSTRACT FROM AUTHOR]