A series of lithium complexes ([Ph₂P(o-C₆H₄-CH₂Li·TMEDA)] (1-Li), [PhP(o-C₆H₄-CH₃)(o-C₆H₄-CH₂Li·TMEDA)] (2-Li), [PhP(o-C₆H₄-CH₂Li·TMEDA)₂] (2-Li₂) and [P(o-C₆H₄-CH₂Li·TMEDA)₃] (3-Li₃)) was prepared from mono-, di- and tri-benzylphosphines and varying amounts of nBuLi and was characterized extensively by IR and ¹H, ⁷Li, ¹³C and ³¹P NMR spectroscopy. The molecular structures of complexes 1-Li and 2-Li were determined by single-crystal X-ray diffraction studies. The two complexes have monomeric structures in the solid state comprising seesaw lithium atoms. In each case, the ligand exhibits an asymmetric C-C η²-coordination mode and an intramolecular P-Li bond interaction. Theoretical calculations at Density functional theory (DFT) level M06/6111+G(2d,p) show that indeed a P-Li bond is established which can be explained as the P lone pair (sp^1.26) being partially delocalized on an available sp² orbital on Li (sp^2.04) and additional bonding contribution of the phosphorous atom to Li stems from further delocalization of a σ P-C orbital into the sp² orbital on Li. The observed short contact distances between an aromatic ipso carbon and Li in the crystal structures of 1-Li and 2-Li are explained as due to the interaction of a σ C-Li orbital into the π* orbital of a C-C aromatic bond. Preliminary tests show compounds 1-Li, 2-Li, 2-Li₂ and 3-Li₃ are active catalysts in the solvent free ring-opening polymerization (ROP) of ε-caprolactone (ε-CL) and rac-lactide (rac-LA). High conversions to polycaprolactones were obtained in short periods of time: 1–6 min at 25 °C. Additionally, all four lithium complexes behave as moderately good initiators for the ROP of rac-LA showing high conversions to polylactides at 140 °C in one hour.