The solvated centrosymmmtric title compound, [Li2(C24H34O4P)2(C10H8N2)2]·2C7H8, was formed in the reaction between {Li[(2,6-iPr2C6H3-O)2POO](MeOH)3}(MeOH) and 2,2′-bipyridine (bipy) in toluene. The structure has monoclinic (P21/n) symmetry at 120 K and the asymmetric unit consists of half a complex molecule and one molecule of toluene solvent. The diaryl phosphate ligand demonstrates a μ-κO:κO′-bridging coordination mode and the 2,2′-bipyridine ligand is chelating to the Li+ cation, generating a distorted tetrahedral LiN2O2 coordination polyhedron. The complex exhibits a unique dimeric Li2O4P2 core. One isopropyl group is disordered over two orientations in a 0.621 (4):0.379 (4) ratio. In the crystal, weak C—H...O and C—H...π interactions help to consolidate the packing. Catalytic systems based on the title complex and on the closely related complex {Li[(2,6-iPr2C6H3-O)2POO](MeOH)3}(MeOH) display activity in the ring-opening polymerization of ∊-caprolactone and L-dilactide.