Hydrogels are materials of interest in the biomedical field due to their potential application in wound dressing as well as in drug delivery devices. This work describes the production of a novel poly(N-vinyl-2-pyrrolidone) (PVP) hydrogel membrane produced by electrospinning with a gel fraction up to 90% and a high swelling degree. PVP electrospun nanofiber, cross-linking with UV-C radiation and Fenton reactions, were used to obtain a highly porous membrane. By a 23 experimental design the control of the nanofiber diameter was achieved and proven to exert significant influence on the BSA release profile. Collagenase release behavior and its enzymatic activity were also evaluated in order to estimate the ability of this biomaterial to be used as an enzymatic debriding wound dressing.