High resoln. solid state 31P NMR spectra are reported of 4 representative examples of metal phosphine complexes. The spectra from a Rh complex (Wilkinson's catalyst) and Cu complexes show splittings due to 31P-metal coupling. In spite of the Cu quadrupole interaction, the 31P NMR lines of the Cu complexes are narrow (.apprx.2 ppm). For 1 Cu complex the splittings between the lines of the 31P quartet are unequal. Also the spectrum of a Au cluster is reported.