Support-free liquid-liquid chromatography (LLC), commonly referred to as countercurrent chromatography (CCC) or centrifugal partition chromatography (CPC), is considered a hybrid technique between liquid-liquid extraction (due to its partitioning separation mechanisms and high loading capacity) and solid-liquid chromatography (due to its very high selectivity). The ‘column’ in LLC is mounted either on a single axis rotor (in CPC) or double axis rotor (in CCC) and it is subjected to a centrifugal field that allows the stationary liquid phase to be kept inside the column, while the mobile liquid phase, immiscible with the first one, is pumped through it. Since there is no solid sorbent, no irreversible adsorption can practically occur, whereas the costs of purification are relatively low, as expensive solid stationary phases, time intensive column packing procedures or high-purity solvents are not required. The tailor-made mannerly preparation of the biphasic solvent systems as well as the numerous operating mode possibilities [classical ascending or descending elution, gradient elution, extrusion elution, recycling elution, continuous elution, (multiple) dual mode elution] make LLC a highly versatile and adaptable separation technique. As applications, examples in which LLC was integrated as a viable platform to isolate highly specific constituents from medicinal plants will be provided.