The synthesis and characterization of a series of bis(phosphinic)diamido yttrium alkoxide, amide, and aryloxide initiators are reported. The new complexes are characterized using multinuclear nuclear magnetic resonance (NMR) spectroscopy, elemental analysis, and, in some cases, X-ray crystallography. The alkoxide complexes are all dimeric in both the solid state and in solution, as are the amide complexes substituted with iso-propyl or phenyl groups on the phosphorus atoms. On the other hand, increasing the steric hindrance of the phosphorus substituents (tert-butyl), enables isolation of mononuclear yttrium amide complexes with either 2,2-dimethylpropylene or ethylene diamido ligand backbones. The complex of 2,6-di-tert-butyl-4-methylphenoxide is also mononuclear. All the new complexes are efficient initiators for rac-lactide ring-opening polymerization. The polymerization kinetics are compared and pseudo first order rate constants, k(obs), determined. The polymerization control is also discussed, by monitoring the number-averaged molecular weight, M(n), and polydispersity index, PDI, obtained using gel permeation chromatography (GPC). The alkoxide complexes are the most efficient initiators, showing very high rates and good polymerization control, behavior consistent with rapid rates of initiation. The phenoxide and amide complexes are less efficient as manifest by nonlinear regions in the kinetic plots, lower values for k(obs), and reduced polymerization control. One of the mononuclear yttrium amide complexes shows heteroselectivity in the polymerization of rac-lactide; however, this effect is reduced on changing the initiating group to phenoxide or on changing the ancillary ligand diamido backbone group.