Beryllium-9 (9Be) quadrupolar coupling and chemical shift tensor data are reported for bis(1-(2,6-diisopropylphenyl)-3,3,5,5-tetramethylpyrrolidine-2-ylidene)beryllium (Be(CAAC)2). These are the first such data for beryllium in a linear dicoordinate environment. The 9Be quadrupolar coupling constant, 2.36(0.02) MHz, is the largest recorded in the solid state to date for this isotope. The span of the beryllium chemical shift tensor, 22(2) ppm, covers about half of the known 9Be chemical shift range, and the isotropic 9Be chemical shift, 32.0(0.3) ppm, is the largest reported in the solid state to our knowledge. DFT calculations reproduce the experimental data well. A natural localized molecular orbital approach has been used to explain the origins and orientation of the beryllium electric field gradient tensor. The single-crystal X-ray structure of a second polymorph of Be(CAAC)2 is also reported. Inspection of the powder X-ray diffraction data shows that the new crystal structure is part of the bulk product next to another crystalline phase. Therefore, experimental X-ray powder data for the microcrystalline powder sample and the SSNMR data do not fully match either the originally reported crystal structure (Arrowsmith et al. Nat. Chem. 2016, 8, 890–894) or the new polymorph. The ability of solid-state NMR and powder X-ray diffraction to characterize powdered samples was thus particularly useful in this work.