A procedure involving anion-exchange solid-phase extraction is used to separate hydrastine and berberine alkaloids found in goldenseal (Hydrastis canadensis) from caffeic (phenolic) acids found in both Echinacea purpurea and goldenseal, prior to HPLC assay of Echinacea purpurea/goldenseal combination formulations. Echinacea alkylamides are separated from the phenolic acids and determined. Several commercial products are assayed.