Despite its importance in drug and material science, spectroscopic characterization of polymorphs or supramolecular structures of paramagnetic systems often poses challenges, particularly for noncrystalline solids. This work demonstrates that C-13 solid-state NMR (SSNMR) of paramagnetic systems under very fast magic angle spinning (VFMAS) (spinning speed of 20 kHz or higher) provides exceptionally sensitive means to probe small structural difference among polymorphs of paramagnetic complexes in noncrystalline solids, including drugs and materials containing paramagnetic metal ions. 13C VFMAS SSNMR experiments and corresponding ab initio shift calculations for Cu(II)(B-quilinolinol)(2), anticancer agents, show that alpha- and beta-forms of this compound can be easily distinguished by notable difference in paramagnetic relaxation times and hyperfine shifts. It is also shown that applications of the present technique allow for quantitative and chemical characterization of solid-state reactions for Cu(8-quilinolinol)(2) and Cu (imidazole)(2) in a noninvasive manner.