Abstract 85,87Rb NMR spectra and relaxation are reported in the temperature range 4–300 K, for samples of C 60 intercalated with Rb through a direct-reaction technique at the nominal composition Rb 3C 60. The NMR spectrum is characteristic of the second-order quadrupole powder distribution of the central line, indicating a local non-cubic symmetry at the Rb site and a very small Knight shift. The relaxation rate is found to follow a T 2 law above 30 K. This result, together with the ratio of the relaxation for the two Rb isotopes, points towards a quadrupole relaxation mechanism by phonons. Two contributions were found in the nuclear magnetization recovery which have been attributed to the Rb nuclei in the tetrahedral site and in the octahedral site, respectively, with the nucleus in the T-site coupled more strongly to the lattice dynamics. No detectable change in the NMR spectrum and/or relaxation rates was found at the superconducting transition located at T c = 27.5 K.