Electrospun nanofiber membranes offer many advantages and their application in drug delivery and regenerative medicine is significant. Solvent based electrospinning processes typically use hazardous organic solvents that not only pose a health hazard to manufacturers and users of electrospinning but could also be trapped in trace amounts within the products that are delivered to the end users. Water‐mediated green electrospinning of a poly(vinyl alcohol) (PVA)/poly(acrylic acid) (PAA) blend and cross‐linking of the nanofiber membrane was attempted by heat treatment. The resulting nanofiber membrane was a polyelectrolyte coated in a layer by layer (LBL) method using poly(ethyleneimine) (PEI)/PAA polymers. The polyelectrolyte coated and uncoated nanofibers were characterized with IR, scanning electron microscopy (SEM), and tensile strength measurements. The SEM images showed the swelling nature of the LBL polyelectrolyte nanofibers or the hydrogel nanofibers. The antimicrobial activity of the membranes was evaluated using the E. coli strain and compared with the polyelectrolyte untreated control. The polyelectrolyte membranes exhibited strong antimicrobial activity in comparison to the control and holds potential application in wound dressing materials or specific applications as wound dressing hydrogel nanofibers.