Polyvinyl alcohol/chitosan (PVA/CS) core-shell nanofibers are successfully fabricated by a simple coaxial electrospinning method, in which PVA forms the core layer and CS forms the shell layer. With the change of the feed ratio between PVA and CS, the surface morphology and the microstructures of the nanofibers are largely changed. The as-prepared core-shell fibers can be used as a carrier for doxorubicin (DOX) delivery. FT-IR analysis demonstrates that hydrogen bond between CS and PVA chains forms. The results of in vitro cytotoxicity test indicate that the core-shell fibers are completely biocompatible and the free DOX shows higher cytotoxicity than the DOX loaded nanofibers. The standing PVA/CS core-shell fibers remarkably promote the attachment, proliferation and spreading of human ovary cancer cells (SKOV3). Via observing by confocal laser scanning microscopy (CLSM), the DOX released from the fibers can be delivered into SKOV3 cell nucleus, which is significant for the future tumor therapy. And, the as-prepared fibers exhibit controlled release for loaded DOX via adjusting the feed ratio between PVA and CS, and the DOX loaded nanofibers are quite effective in prohibiting the SKOV3 ovary cells attachment and proliferation, which are potential for chemotherapy of ovary cancer.