Ab initio calculations have been carried out in a systematic investigation of P···N pnicogen complexes H₂XP:NXH₂ for X ═ H, CH₃, NH₂, OH, F, and Cl, as well as selected complexes with different substituents X bonded to P and N. Binding energies for complexes H₂XP:NXH₂ range from 8 to 27 kJ mol^–1 and increase to 39 kJ mol^–1 for H₂FP:N(CH₃)H₂. Equilibrium structures have a nearly linear A–P–N arrangement, with A being the atom directly bonded to P. Binding energies correlate with intermolecular N–P distances as well as with bonding parameters obtained from AIM and SAPT analyses. Complexation increases ³¹P chemical shieldings in complexes with binding energies greater than 19 kJ mol^–1. One-bond spin–spin coupling constants ^1pJ(N–P) across the pnicogen interaction exhibit a quadratic dependence on the N–P distance for complexes H₂XP:NXH₂, similar to the dependence of ^2hJ(X–Y) on the X–Y distance for complexes with X–H···Y hydrogen bonds. However, when the mixed complexes H₂XP:NX′H₂ are included, the curvature of the trendline changes and the good correlation between ^1pJ(N–P) and the N–P distance is lost.