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Supported liquid membrane (SLM) and solid phase extraction (SPE) have been applied as clean-up and/or enrichment techniques for a mixture of five benzimidazole anthelmintics compounds, namely albendazole, fenbendazole, mebendazole, oxibendazole, and thiabendazole. Two biological matrices, mainly urine and milk, and ultra high purity (UHP) water were spiked with a mixture of these five compounds. Waters Oasis (R) MCX and International Sorbent Technology (IST) HCX SPE sorbents were used. The liquid membrane used for clean-up and/or enrichment of these compounds was 5% tri-n-octylphosphine oxide (TOPO) dissolved in n-undecane/di-n-hexyl ether (1: 1). The SLM extraction efficiencies and SPE percentage recoveries ranged between 60 and 100%. The detection limits (DLs) for different benzimidazole compounds by SPE/LC-ES-MS for thiabendazole, oxibendazole, and albendazole was 0.1 ng/L, for fenbendazole and mebendazole was I and 10 ng/L, respectively. Similarly, the detection limits of SLM/LC-ES-MS for thiabendazole, oxibendazole, and albendazole was 0.1 ng/L and for fenbendazole and mebendazole was I ng/L. The results of optimization of various parameters of the SLM method are reported. (c) 2005 Elsevier B.V. All rights reserved.