A simple and sensitive microemulsion extraction separation method was developed for the speciation of aluminium in tea samples by spectrofluorimetry. With 8-hydroxyquinoline (8-HQ) as the chelating agent and Triton X-100 Winsor II microemulsion as the extractant, separation of aluminium species in different pH solutions was achieved by microemulsion extraction. The formation of microemulsion, the conditions of extraction and determination of aluminium species were studied. The results showed that, the contents of aluminium species in tea leaves and infusions samples, such as total aluminium, total soluble aluminium, total granular aluminium, inorganic aluminium except Al-F, and (Al-F + Al-org), were obtained successfully under the optimal conditions. The limit of detection was 0.23 mu g L-1 in pH 9.5 solution, and 0.59 mu g L-1 in pH 6.0 solution respectively; the precision (RSD) for 11 replicate measurements of 10 mu g L-1 aluminium was 2.1% in pH 9.5 solution, and 2.8% in pH 6.0 solution respectively; the recoveries for the spiked samples were 96.8-103.5%. The proposed method is simple and efficient, which has been applied to the speciation of aluminium in tea samples with satisfactory results. (C) 2010 Elsevier B.V. All rights reserved.