Excellent water-absorbing nanofiber meshes were developed as a potential material for removing excess fluids from the blood of chronic renal failure patients toward a wearable blood purification system without requiring specialized equipment. The nanofiber meshes were successfully fabricated from poly(acrylic acid) (PAA) under various applied voltages by appropriately setting the electrospinning conditions. The electrospun PAA nanofibers were thermally crosslinked via heat treatment and then neutralized from their carboxylic acid form (PAA) to a sodium carboxylate form poly(sodium acrylate) (PSA). The PSA nanofiber meshes exhibited a specific surface area 393 times that of the PSA film. The PSA fiber meshes showed a much faster and higher swelling than its corresponding film, owing to the higher capillary forces from the fibers in addition to the water absorption of the PSA gel itself. The proposed PSA fibers have the potential to be utilized in a new approach to remove excess water from the bloodstream without requiring specialized equipment.