We have developed a Nuclear Magnetic Resonance (NMR)-based approach to metabolomics research that enables the identification of bioactive compounds in crude plant extracts. For this work, we used black raspberries, which are known to contain compounds that exhibit chemopreventive activity toward oral, esophageal, and colon cancers. To ascertain bioactive components and their interrelationships, NMR results for black raspberry samples from four cultivars grown on commercial farms in Ohio were examined using principal component analysis. Multivariate analysis that included anthocyanin content (HPLC), antioxidant activity (DPPH, ABTS, FRAP), total phenolics (Folin-Ciocalteau assay), and bioactivity as measured by inhibition of colon cancer HT-29 cell line proliferation showed correlations with specific regions of NMR spectra at 400 MHz. Correlations were also observed for major and minor groupings of the black raspberry samples. Replicate black raspberry samples were examined with a 750 MHz NMR spectrometer equipped with a cryoprobe that provided a 4- to 5-fold improvement in sensitivity. In this manner, even minor bioactive components in black raspberries could be examined to determine additive and synergistic effects.