Ph2PCl easily inserts into the Ta-H bond of Cp(2)TaH(3) affording an ionic complex [Cp(2)TaH(2)(HPPh(2))]Cl (4). This species was deprotonated to give the first phosphido-substituted tantalocene complex Cp(2)TaH(2)PPh(2) (5), which was characterized by NMR spectroscopy and X-ray crystallography. Thermal decomposition of 5 as well as its reaction with HPPh(2) was studied.