The results of a systematic solid-state (31)P NMR study of 5-phenyldibenzophosphole, DBP, its chalcogenides, and some of its transition metal complexes are reported. Phosphorus chemical shift tensors have been obtained from (31)P NMR spectra of stationary samples and of samples spinning about the magic angle. The spans of the phosphorus chemical shift tensors for DBP and its chalcogenides are comparable to those of the corresponding compounds of triphenylphosphine; however, the asymmetry of the tensors for the DBP series reflects the reduced local symmetry at phosphorus. For the complexes (DBP)M(CO)(5) and cis-(DBP)(2)M(CO)(4), where M is a group 6 transition metal (Cr, Mo, W), the most shielded component of the phosphorus shift tensor is found to be relatively independent of the metal or complex, delta(33) = -41 +/- 8 ppm, and is thought to lie along or close to the P-M bond axis direction. In contrast, delta(11) and delta(22) show considerable variation but decrease systematically on descending the group from Cr to W. Group 10 metal complexes, (DBP)(2)MX(2), have also been investigated, including several trans geometric isomers of nickel, cis and trans isomers of palladium, and cis isomers of platinum. The phosphorus shift tensors are nonaxially symmetric with spans in the range 50 -150 ppm. The phosphorus shift tensors of the two nonequivalent DBP ligands of (DBP)(2)PtX(2) (X = Cl, Br) exhibit quite different principal components. The intermediate component of the shift tensor is thought to lie along the Pt-P bond in these complexes. Some of the complexes exhibit interesting MAS-frequency-dependent (31)P NMR spectra.