The mixed Sb/Bi compounds necessitated the use of the variable offset cumulative spectra (VOCS) acquisition approach to ensure consistent excitation of the broad 121 Sb NMR powder patterns that formed upon mixing Sb and Bi (i.e., the medium-range order was reduced, resulting in an increase of the electric field gradient about Sb). The non-spinning 121 Sb NMR spectra for Li3Sb0.75Bi0.25 and Li3Sb0.50Bi0.50 clearly indicate multiple Sb medium-range environments with evidence of second-order quadrupole broadening that is induced by the Sb/Bi mixing in the M position, with the broadest resonance (fwhm = ~115 kHz) attributed to the Li3Sb0.50Bi0.50 compound, consistent with this composition having random M-site Sb/Bi mixing.