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The phase-separation phenomenon of non-ionic surfactants occurring in aqueous solution was used for the extraction of cadmium(II), lead(II), palladium(II) and silver(I). The analytical procedure involved the formation of understudy metals complex with bis((1H-benzo [d] imidazol-2yl)ethyl) sulfane (BIES), and quantitatively extracted to the phase rich in octylphenoxypolyethoxyethanol (Triton X-114) after centrifugation. Methanol acidified with 1molL⁻¹ HNO₃ was added to the surfactant-rich phase prior to its analysis by flame atomic absorption spectrometry (FAAS). The concentration of BIES, pH and amount of surfactant (Triton X-114) was optimized. At optimum conditions, the detection limits of (3sdb/m) of 1.4, 2.8, 1.6 and 1.4ngmL⁻¹ for Cd²⁺, Pb²⁺, Pd²⁺ and Ag⁺ along with preconcentration factors of 30 and enrichment factors of 48, 39, 32 and 42 for Cd²⁺, Pb²⁺, Pd²⁺ and Ag⁺, respectively, were obtained. The …