The repair and regeneration of bone is one of the major problems of clinical medicine. In this study, we first synthesized the epoxidized methyl oleate-Graphite oxide (EMO-GO), and the EMO-GO/Poly(L-lactide) fibrous scaffolds were successfully prepared through electrospinning. The hybrid fibers exhibited improved hydrophobicity compared to corresponding blank Poly(L-lactide) fibers. The prepared EMO-GO/Poly(L-lactide) fibrous scaffolds favored mesenchymal stem cells (MSCs) attachment and proliferation though provision of three-dimensional porous environment. Meanwhile, MSCs can penetrate into the fibrous scaffolds through the interstitial pores and integrate well with the fibers, which is a very vital factor for their application in tissue engineering. After transplantation into the thigh muscle pouches of rats, we evaluated the acute toxicity of EMO-GO/Poly(L-lactide) electrospun in vivo and the scaffolds presented good biocompatibility. Based on the good in vitro cellular response, as well as their biocompatibility with the organ in vivo, the EMO-GO/Poly(L-lactide) hybrid fibrous scaffolds can be one of the most promising candidates in bone tissue engineering.