The 13C, 27Al and 11B NMR spectra of tri(tert-butyl)alane, AlBut3, and of the corresponding borane, BBut3, respectively, were examined in order to determine the magnitude of the coupling constants 1J(27Al,13C) = 94±5 Hz and 1J(13C,11B) = 52±2 Hz by measurement of the line widths of the 13C NMR signals and of the relaxation rates of the quadrupolar 27Al and 11B nuclei. This is the first example of 1J(27Al,13C) determined for a monomeric trialkylalane. In addition, the coupling constants were calculated by DFT methods (B3LYP) using the 6-311+G(d,p) basis set. The 1H, 13C and 27Al NMR spectra of lithium tetra(tert-butyl)alanate, Li[AlBut4], were measured under various conditions. Ion-pair separation in THF revealed the expected patterns for 27Al-13C spin-spin coupling across one and two bonds as well as for the three-bond 27Al-1H spin-spin coupling.