The non-chromatographic strategy developed for As(V), As(III), Sb(V) and Sb(III) determination by HG-AFS offers an alternative simple and fast speciation analysis of inorganic forms of As and Sb in milk samples which provides data comparable with those obtained for total As and Sb in milk by ICP-MS after microwave-assisted sample digestion. It is demonstrated that sample sonication at room temperature with aqua regia does not modify the oxidation state of As and Sb species in commercial samples.