The aim of this work is to develop an on-line coupling of electrochemical pre-concentration to atomic absorption spectrometry (AAS) method and the utilization of the developed system for the determination of ultra-trace amounts of Sb in water samples. A flow-through electrochemical analyzer EcaFlow (model GLP 150, Istran, Bratislava) was used as the pre-concentration unit with a two-electrode cell. The working electrode was an RVC electrode coated with gold. An AAS spectrometer SP9 with a graphite furnace atomizer (Pye Unicam) was used to measure the pre-concentrated Sb species. The pre-concentration parameters for the electrochemical process were optimized. Moreover, the determination of Sb by graphite furnace atomic absorption spectrometry (GFAAS) was optimised enabling a direct measurement also from HCl media. The pre-concentration step was optimised and characterised.