In this report, the In and 209 Bi solid-state NMR spectra and quadrupolar parameters of three recently discovered complex oxides (LiIn 2 SbO 6 , BiAlTeO 6 , and BiGaTeO 6 ; Figure ) are examined via (ultra-)wideline NMR, periodic DFT calculations, and numerical modeling. LiIn 2 SbO 6 is a rutile-like structure with a channel arrangement that is unique amongst rutile phases (Figure ). BiAlTeO 6 and BiGaTeO 6 are isostructural layered compounds with alternating pure BiO 6 and mixed, ordered MO 6 /TeO 6 (M = Al, Ga) (Figure ). Collection of the broad (>15 MHz) NMR spectra is facilitated by signal enhancement from the quadrupolar Carr-Purcell-Meiboom-Gill (QCPMG) pulse sequence in combination with frequency-stepped acquisition, also known as the variable-offset cumulative spectrum (VOCS) Solid-state NMR. NMR spectra were recorded in a 9.4 T static magnetic field with a Bruker