δ(31P) NMR data of the complexes [Nb(Cp)(CO)3PZ3] (Cp = η5-C5H5) and cis- [Nb(Cp)(CO)2(PZ3)2] [Z = H, R (alkyl and aryl), OR, NMe2, PR2] are interpreted on the basis of varying P(3pσ) and P(3dπ) contributions to the bond-order density matrix in the paramagnetic deshielding term of the overall shielding constant. For Z = R, shielding of the 31P nucleus of the coordinated phosphine decreases as the cone angle θ increases, as a result of increasing p contribution. For Z = OR and NMe2, P-Nb π interactions dominate, and the decrease of the P(3dπ) occupation with increasing θ leads to an increase of shielding. In the case of alkoxiphosphines, decreasing 31P shielding is accompanied by an increase of the shielding of the metal nucleus [quantified here by δ(51V) of the vanadium complexes], while, for the substantially less powerful π interacting alkylphosphines, shielding trends for the two nuclei parallel each other. Coordination shifts Δδ(P) are somewhat greater for small phosphines but, spanning a range of 80 ± 30 ppm, tend to be comparatively invariant. In [V(Cp)(CO)3PZ3], the 31P nucleus is deshielded by 10 to 30 ppm with respect to the corresponding niobium complexes.