In this study, we successfully constructed the new graphene oxide/poly-L-lactic acid (GO/PLLA) nanofiber scaffolds with a hydrophilic surface and porous network structure that were highly favorable for cell infiltration. When employed these new nanofiber scaffolds for a wide range of tissue engineering applications, it was expected to promote graft tissue survival and angiogenesis. The new GO/PLLA nanofiber scaffold with an appropriate concentration of 1.0 wt% was applied for the restoration of ovarian function and reserve in mice with primary ovarian insufficiency (POI). After co-transplanting the normal ovarian cortex loaded on these new nanomaterials into the in situ ovarian tissue of POI mice, the fusion of transplanted ovarian cortex with damaged ovarian tissue was improved, as well as the ovarian function and the follicle numbers. Moreover, angiogenesis was observed clearly and proved to exist in the transplanted tissue and nanomaterials, with the most conspicuous effect after co-transplantation with 1.0 wt% GO/PLLA nanofiber scaffold. In addition, nitric oxide (NO) production by phosphorylated endothelial nitric oxide synthase (p-eNOS) in vivo was proven to be involved in the effect of GO and PLLA on the improved survival rate of the transplanted ovarian cortex. This study provides a new method for the fertility preservation of ovarian tissue cryopreservation and transplantation, as well as a new strategy for the transplantation of other organs.