We show that Ga-Se through-bond connectivities can be analyzed by ssNMR in crystalline b-Ga2Se3. We show that two 2D methods can be used for such analysis: J-RINEPT and J-HMQC. We demonstrate that the evolution of the build-up curves versus the evolution times can be used to quantify the various JGa-Se values, even in three-dimensional network compounds. We also compare the efficiencies and resolutions of J-RINEPT, J- and D-HMQC 2D methods used to determine the Ga-Se through-bond and through-space connectivities. Then, we apply these 2D methods to the chalcogenide glass system made with the Ga2Se3-GeSe2 binary system,1,2 and we show that by fitting all these 2D results, so that the 1D-CPMG spectra, we obtain a detailed structural description of this glass.3