Reverse micelles extraction technology are efficient and economical alternative for extraction of bioactive molecules due to its high selectivity, fast mass transfer and relatively low cost. In this study, AOT can form wide range of reverse micellar core sizes in organic phase, which has been used to extract tea polysaccharides (TPS) in AOT/heptane reverse micellar system. Process conditions were optimized by pH, types and concentration of salts, types and concentration of alcohols. Chaotropes (GuHCl and urea) were used to improve extraction yield of tea polysaccharides in the system. In forward extraction, low concentration of GuHCl in this AOT/heptane system may influence the TPS structure and suppress its aggregation formation and promote its solubilization into the water cores. Under optimal conditions (pH 4.6, 0.05 mol L-1 NaCl, 7% [v/v] methanol and 0.06 mol L-1 GuHCl), the forward extraction recovery reached 34%. In backward extraction, 100% of backward recovery was achieved by adding GuHCl or urea. (c) 2013 Elsevier B.V. All rights reserved.