A series of polyvinyl alcohol (PVA), PVA/chitosan (CS) and PVA/cyanobacterial extracellular polymeric substances (EPS) blended nanofibrous membranes were produced by electrospinning using a microfiltration poly(vinylidene fluoride) (PVDF) basal membrane, for potential applications in water filtration. Nanofibres were obtained from solutions of 20% (w/w) PVA with 1% (w/w) CS or EPS, using a weight ratio of 60/40. Blended nanofibres have shown a smooth morphology, no beads formation and diameters between 50 and 130 nm. Thermo-mechanical analysis demonstrated that there were inter and/or intramolecular hydrogen bonds between the molecules of PVA/CS and PVA/EPS in the blends. The electrospun blended PVA/EPS membrane showed better tensile mechanical properties when compared with PVA and PVA/CS, and resisted more against disintegration in the temperature range between 10 and 50 degrees C. Finally, the blended membranes have shown an increase in chromium binding capacity of 5%. This is the first successful report of a blended membrane of electrospinned cyanobacterial polysaccharide with PVA. (C) 2013 Elsevier Ltd. All rights reserved.