Antimony is a widely distributed trace element of ecotoxicological interest. A pathway via bioalkylation of inorganic Sb species is discussed in the literature, resulting in organically bound Sb species. Therefore, Sb speciation becomes increasingly a matter of interest for risk assessment in the environment. This contribution investigates the possibilities of CE on-line hyphenated to ICP–MS for Sb speciation. Two methods are employed, both highly resolving the species but only one preserving the species stability. The latter used Na 2HPO 4/ NaH 2PO 4, 20 m M, pH 5.6 as the background electrolyte and NaOH or acetic acid as stacking electrolyte 1 or stacking electrolyte 2, respectively. Detection limits of 0.1 μg/l–0.7 μg/l, depending on species, were achieved. When analysing liquid phases from fouling and sewage sludge up to eight antimony species were detected. Sb (V) as well as methylated Sb species were found.