Bioactive natural products are major sources of lead compounds for drug discovery and pharmaceutical development, therefore, innovative and current separation and characterization techniques are important for these compounds. Here, CE methods applied for the analysis of natural products published during 2011–2012 are reviewed. This is an updated version of an earlier review paper in this journal, which highlighted developments during 2006–2010. The major method developments over the review period centered on derivatization, chiral analysis, modes of detection, stacking or on-line sample concentration, and sample preparation (predominantly using extraction methods). The samples analyzed were herbal products, foods, soil, and biological samples. Developments also occurred in the areas of quality control, toxicology assessment, and enzyme-inhibitor screening. A table that summarizes the areas, source of natural product, nature of the bioactive analyte, CE conditions, LODs, and corresponding reference is provided. A short description on the theory of CE and insights on future activities of CE on natural products are also presented.