Triamidoamine-supported zirconium complexes catalyze the heterodehydrocoupling of primary phosphines with silane and germanes. In this catalysis, P-Si or P-Ge products are observed exclusively with no competitive P-P bond formation. Phosphido complexes (N3N)ZrPHR (N3N = N(CH2CH2NSiMe3)(3)(3-), R = Ph, 2; Cy, 3) were observed to be the catalyst resting state, and complex 2 was structurally characterized.