The preparation and structural characterization of tantalum complexes supported by 2,2′-phenylphosphino-bis(4,6-di-tert-butylphenolate) (OPO2−) are described. The reaction of Li2OPO with TaCl5, regardless of the molar ratio employed, in diethyl ether at −35 °C led to high-yield isolation of yellow crystalline OPO2TaCl. Alkylation of OPO2TaCl with MeMgBr or EtMgCl in diethyl ether at −35 °C generated the corresponding alkyl complexes OPO2TaR (R = Me, Et). Thermolysis of OPO2TaEt in benzene led to quantitative formation of OPO2TaH, which could also be prepared by treatment of OPO2TaCl with LiHBEt3 in diethyl ether at −35 °C. Hydrolysis of OPO2TaCl or OPO2TaR (R = H, Me, Et) generated OPO2TaOH. The reaction of OPO2TaOH with Me3SiCl in diethyl ether at room temperature afforded quantitatively OPO2TaCl. The solution structures of these complexes were all characterized by multinuclear NMR spectroscopy. The solid-state structures of OPO2TaCl, OPO2TaH, and OPO2TaOH were determined by X-ray crystallography. The spectroscopic and crystallographic data are all indicative of the coordination of both phosphorus donors to tantalum in these 7-coordinate complexes. Interestingly, the structure of OPO2TaH is markedly different from those of OPO2TaX (X = Cl, OH, Me, Et) on the basis of NMR and X-ray studies. Density functional theory computations reveal that the hydride structure found by X-ray crystallography is lower in energy by about 7 kcal/mol than that analogous to the established X-ray structures of OPO2TaCl and OPO2TaOH.