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Cd(OH)2 nanowires have been synthesised in high yield based on a supported liquid membrane (SLM) system for the first time. X-ray powder diffraction, scanning electron microscopy and transmission electron microscopy were employed to characterise the product, which revealed that the product mainly consisted of woven Cd(OH)2 nanowires with diameters ranging from several nanometres to about 50 nanometres. The UV-vis spectrum indicated that the as-obtained Cd(OH)2 nanowires had a direct bandgap of 4.25 eV, which was larger than the value for Cd(OH)2 nanoplates prepared by direct precipitation and meaned more efficient photocatalytic activity for nanoscale effect. The results of photocatalytic activity experiments showed that the Cd(OH)2 nanowires, compared to Cd(OH)2 nanoplates prepared by direct precipitation, were more effective to degradation of rhodamine B (RhB) dye under irradiation of ultraviolet light. This method based on SLM may be applied in coupling preparing functional nanomaterials and treatment of both heavy metal ions wastewater and high-alkaline wastewater containing organic contaminants.