Water pollution is a serious concern for public health and environment in today's world; hence, there exists a strong demand to develop cost-effective, sustainable and eco-friendly membranes. Here, we produce a highly efficient molecular filter membrane based on bio-renewable material; cyclic oligosaccaharides known as cyclodextrins (CD). Crosslinked insoluble poly-CD nanofibers are produced by using electrospinning technique in the absence of any additional polymeric carrier. Poly-CD nanofibrous membrane exhibit significant affinity to a common class of organic pollutant (i.e. methylene blue (MB)). Remarkably, the electrospun poly-CD nanofibrous web can outdistance the commonly used filter material (i.e. activated carbon) in terms of removal capacity. The flexible and free-standing poly-CD nanofibrous membrane depicted outstanding filtration performance. We estimate of above 90% removal efficiency for highly concentrated solutions of MB pollutant (40 mg/L) under extremely high flux (3840 Lm(-2)h(-1)). Essentially, these poly-CD nanofibrous webs demonstrate quite rapid uptake of MB from liquid environment. Overall, bio-based flexible electrospun poly-CD nanofibrous membrane represents a highly efficient molecular filter for wastewater treatment.