The trimethylphosphine complex Ta(PMe₃)₂Me₃Cl₂ has been synthesized by addition of PMe₃ to TaMe₃Cl₂. The molecular structures of both TaMe₃Cl₂ and Ta(PMe₃)₂Me₃Cl₂ have been determined by X-ray diffraction thereby demonstrating that, in the solid state, these complexes respectively adopt trigonal bipyramidal and capped trigonal prismatic geometries.