Arsenic contamination in drinking water is a serious problem worldwide. In this study, to remove arsenate from contaminated water, a new thin-film composite (TFC) membrane was fabricated and tested. This membrane was composed of an electrospun nanofibrous scaffold, a polyethylene terephthalate (PET) substrate as support, and a polyacrylonitrile (PAN) coating layer. To effectively reject arsenate ions, cetylpyridinium chloride (CPC) pretreatment was used. For evaluating the performance of TFC membrane, its flux and contaminant rejection were compared to a conventional ultrafiltration (UF) membrane. Due to high porosity, the TFC membrane showed a flux, which was 172–520% higher than the UF membrane. In addition, The TFC membrane was 1.1–1.3 times more efficient in rejecting arsenate ions than the UF membrane.