Characterization of paramagnetic compounds, in particular regarding the detailed conformation and electronic structure, remains a challenge - still today it often relies solely on the use of X-ray crystallography, thus limiting the access to electronic structure information. This is particularly true for lanthanide elements that are often associated with peculiar structural and electronic features in relation to their partially filled f -shell. Here, we showcase the use of state-of-the-art magnetic resonance spec- troscopy (EPR and solid-state NMR) and computational approaches as well as magnetic susceptibility measurements to determine the structure of a paramagnetic Yb(III) alkyl complex, Yb(III)[CH(SiMe3)2]3, that features a notable structure according to X-ray crystallography. Each of these techniques revealed specific information about the geometry and electronic structure of the complex; taken together, they provide a detailed understanding of this paramagnetic compound. Namely, this complex displays a three-centre-two-electron Yb-γ-Me-β–Si secondary metal-ligand interaction, whose NMR spectroscopic signature was acquired for the first time for a lanthanide paramagnetic species. The electronic configuration of Yb(III)[CH(SiMe3)2]3 is demonstrated to be close to the one of the free Yb(III) ion, with the partially filled f -shell of the Yb atom having little influence on its bonding properties and with minimal delocalization of f -electron density from Yb to the directly bonded carbons.