This study successfully constructed graphene oxide/poly-L-lactic acid (GO/PLLA) nanofiber scaffolds with a hydrophilic surface and porous network structure, promoting cell infiltration, graft tissue survival, and angiogenesis. A 1.0 wt% GO/PLLA scaffold improved the fusion of transplanted ovarian cortex with damaged ovarian tissue in mice with primary ovarian insufficiency (POI), enhancing ovarian function and follicle numbers. Angiogenesis was observed, and nitric oxide (NO) production by phosphorylated endothelial nitric oxide synthase (p-eNOS) was implicated in the improved survival rate. This offers a new method for ovarian tissue cryopreservation and transplantation and a potential strategy for other organ transplants.