In this work, solid phase extraction (SPE) using nano-sized TiO2 as a solid sorbent was used for separation/preconcentration of total inorganic antimony (iSb) before its determination by electrothermal atomic absorption spectrometry (ETAAS). After adsorption of iSb onto nano-sized TiO2, direct TiO2-slurry sampling was used for sample injection into a graphite tube. The conditions for the reliable slurry sampling together with careful control of the temperature program for the slurry solutions were worked out. Extraction conditions for both inorganic antimony species (Sb(III) and Sb(V)) and interference studies of coexisting ions were studied in detail. The accuracy of the optimized method was checked by the certified reference material (CRM) for trace elements in lake water TMDA-61. Finally, the optimized method was used for the determination of trace inorganic antimony in synthetic and natural waters.