Nano γ-alumina, with ultra-high specific surface area (387.2 m2 g-1), has been synthesized and used as a promising adsorbent material in solid-phase extraction. A simple, sensitive, and economic method was developed for speciation of inorganic antimony by slotted tube atom trapping flame atomic absorption spectrometry (STAT-FAAS) after flow injection on-line nano γ-alumina micro-column solid-phase extraction. In this method, Sb(III)-diethyldithiocarbamate (DDTC) complexes produced on-line from DDTC and Sb(III) were adsorbed by the synthesized γ-alumina nanoparticles in a micro-column, then eluted by 1.0 mol L-1 HNO3 in methanol, whereas Sb(V) remained in aqueous solution. The total inorganic Sb was determined by the same procedure after Sb(V) was reduced with thiourea. Under optimal conditions, the enrichment factor was 56.5 and the detection sensitivity was improved 40-fold for antimony by STAT-FAAS compared to conventional FAAS. The limit of detection was 6.0 ng L-1 for Sb(III) and 8.2 ng L-1 for Sb(V), respectively. The intra-day precision (RSDs, n = 11) were 2.8 % for Sb(III) and 3.5 % for Sb(V), respectively, and the inter-day precision (n = 3) were 7.1 % for Sb(III) and 8.4 % for Sb(V), respectively. The recoveries for the spiked samples were 93-107 %. The proposed method was applied to speciation of inorganic antimony in water and food samples successfully. ©Springer Science+Business Media New York 2012.