Countercurrent Chromatography (CCC) provides the natural product chemist with a high-resolution separatory method, which is uniquely applicable to sensitive (unstable) compounds and which allows virtually quantitative recovery of the load sample. Different instruments use different means of retaining a stationary liquid phase. The solvent system (SS) can be chosen to optimize the separatory power and the number of systems available is limitless. Several examples are provided to illustrate the power of the method and to guide the chemist in choice of an appropriate SS.