A new [O2N2N′2] 1,4,8,11-tetraazacyclotetradecane-based bis(phenol) chelate, H2(Me2ArO)2Me2-cyclam (2), containing methyl groups in the phenolate rings, has been synthesized and fully characterized. The studies of the coordination chemistry of the hexadentate dianionic ligands, (R2ArO)2Me2-cyclam2− (R=tBu, Me), with [YbI2(thf)2.5] are reported. The reaction of K2(tBu2ArO)2Me2-cyclam with [YbI2(thf)2.5] in 1:1 ratio in thf led to the formation of a divalent ytterbium complex that is highly unstable and propitious to the formation of Yb(III) species, while the metathesis reaction of the less bulky ligand (Me2ArO)2Me2-cyclam2− with [YbI2(thf)2.5] showed a preference for the stabilization of polynuclear divalent ytterbium complexes. The reaction of the potassium salt of this ligand, K2(Me2ArO)Me2-cyclam, with 1.5 and 2equiv. of [YbI2(thf)2.5] in thf led to formation of [Yb3(μ-{(Me2ArO)2Me2-cyclam})2I]I (4) and [Yb2(μ-{(Me2ArO)2Me2-cyclam})I2(thf)2] (5), respectively. The trimer (4) and dimer (5) were characterized by elemental analysis, UV–Vis and NMR spectroscopy and single-crystal X-ray diffraction. These are the first examples of ytterbium(II) complexes incorporating bis(phenolate) cyclam ligands.