Porous nanofiber-microsphere mats of collagen (COL)/polyvinyl alcohol (PVA) containing salicylic acid (SA) as model drug were prepared by electrospinning for the assessment of drug delivery system. The electrospun fibrous mats were crosslinked by UV-radiation or glutaraldehyde to weaken the degree of drug burst release and morphology damage when meeting water. The morphology and chemical structures of COL/PVA-SA electrospun fibers were characterized by SEM and FTIR. The crosslinking of UV-radiation did not destroy the morphology of COL/PVA-SA electrospun fibers in the crosslinking process, however, the crosslinking of glutaraldehyde did it. In vitro release studies showed that COL/PVA-SA electrospun fibers efficiently controlled the release of drugs by the crosslinking of UV-radiation for 4 h. The transport mechanism that controlled the release of drugs from electrospun mats was Fickian diffusion.