Mechanically robust, non-toxic polymer fiber mats are promising materials for a range of biomedical applications; however, further research into enhancing polymer selection is needed. In this study, poly(allylamine) (PAH), an amine-containing polyelectrolyte, was successfully electrospun from aqueous solutions into continuous, cylindrical fibers with a mean diameter of 150 ± 41 nm. A one-step crosslinking method using glutaraldehyde provides insight into the chemical and morphological changes that result from altering the molar ratio of amine to aldehyde groups, whereas a two-step crosslinking method yielded chemically and mechanically robust mats. These results indicate PAH fibrous mats synthesized from aqueous solutions could potentially be applied in biomedical applications.