Herein, we report the first detailed study of Bi-209 solid-state NMR (SSNMR) spectroscopy of extremely broad central transition powder patterns. Bi-209 ultrawideline SSNMR spectra of several bismuth-containing materials (bismuth oxyhalides, bismuth nitrate pentahydrate, nonaaquabismuth triflate, and bismuth acetate) were acquired at field strengths of 9.4 and 21.1 T using frequency-stepped techniques. The Bi-209 SSNMR experiments at 9.4 T yield powder patterns with breadths ranging from 0.9 to 14.6 MHz, from which quadrupolar coupling constants, C-Q(Bi-209), between 78 and 256 MHz, were extracted via analytical simulations. The breadths of the quadrupolar-dominated spectra and overall experimental times are greatly reduced for experiments conducted at 21.1 T, which yield high signal-to-noise spectra in which the smaller effects of bismuth chemical shift anisotropy can be clearly observed. The Bi-209 electric field gradient (EFG) and chemical shift (CS) tensor parameters extracted from these spectra are correlated to the molecular structures at the bismuth sites, via first principles calculations of Bi-209 EFG and CS tensors performed using CASTEP for periodic solids and Gaussian 03 for molecular clusters. The rapidity with which Bi-209 SSNMR spectra can be acquired at ultrahigh fields, the sensitivity of the Bi-209 NMR parameters to the bismuth environment, and the predictive power of theoretically calculated NMR interaction tensors suggest that Bi-209 SSNMR may be useful for the characterization of a variety of Bi-containing materials and compounds.