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Poly(ionic liquid)s nanofiber (PIL NF) membrane was derived from polyacrylonitrile by converting its cyano groups to imidazoline moieties via cyclization with ethylenediamine, followed by quaternization with 1-bromobutane. The novel PIL NF is further decorated with photocatalyst phosphotungstic acid PW12 via anion exchanging to give PW-PIL. The degradation rate of the novel supported photocatalyst towards methyl orange irradiated under visible light was found to be 98%. In addition, the nanofiber membrane morphology is beneficial for easy recycling, and 98% of original degradation rate was maintained after 5 cycles of photocatalysis degradation. This robust, efficient, and recyclable material offers a new approach for serving as catalyst supporter. The photocatalyst PW-PIL is reported for the first time. The inexpensive functional membrane is used to exploit the sun as a cheap and clean source of light.