Metal-metal bonds can be difficult to characterize directly. We demonstrate that J couplings between metal nuclei experiencing strong quadrupolar interactions can be easily measured from well-defined splittings in NMR spectra of powdered samples. Using (69/71)Ga NMR, it is shown that homonuclear J coupling, which is four orders of magnitude smaller than the quadrupolar coupling in a series of compounds featuring gallium-gallium bonds, can be extracted with a 2-D NMR experiment. The dependence of the multiplets on crystal symmetry reveals information on the structures of two Ga-Ga-bonded compounds for which diffraction data are unavailable. Interpretation of the data in a molecular orbital framework provides insight into the nature of the metal-metal bond.