Multiconfigurational, intermediate valent ground states are established in several methyl-substituted bipyridine complexes of bis(pentamethylcyclopentadienyl)ytterbium, Cp-2*Yb (Me-x-bipy). In contrast to Cp-2*Yb(bipy) and other substituted-bipy complexes, the nature of both the ground state and the first excited state are altered by changing the position of the methyl or dimethyl substitutions on the bipyridine rings. In particular, certain substitutions result in multiconfigurational, intermediate valent open-shell singlet states in both the ground state and the first excited state. These conclusions are reached after consideration of single-crystal X-ray diffraction (XRD), the temperature dependence of X-ray absorption near-edge structure (XANES), extended X-ray absorption fine-structure (EXAFS), and magnetic susceptibility data, and are supported by CASSCF-MP2 calculations. These results place the various Cp-2*Yb(bipy) complexes in a new tautomeric class, that is, intermediate-valence tautomers.