The integration of conventional carbonaceous materials with advanced two-dimensional graphene is a challenging but worthwhile attempt to introduce innovative properties into new composites. Herein, we report a novel and facile strategy to create graphene wrapped electrospun carbon nanofiber (GwC) membranes through the surface-induced assembly of graphene oxide (GO) on the surface of pre-oxidized electrospun PAN (oPAN) nanofibers and subsequent carbonization. Driven by the hydrogen bonding between oxygen-containing groups of GO and tertiary amino groups of oPAN, GwC composite membranes with significantly reinforced electrical conductivity are obtained in which every single oPAN fiber is tightly and evenly wrapped by graphene sheets. Additionally, the GwC membrane is further considered as a free-standing template for an in situ growth of few-layered MoSe 2 nanosheets. Compared with the graphene-free counterparts, GwC-MoSe 2 composites exhibit a superior electrochemical hydrogen evolution reaction (HER) performance in both acidic and alkaline solutions due to the highly conductive GwC backbone, thus endowing the newly designed GwC membranes with various possibilities for applications in energy-related fields. † Electronic supplementary information (ESI) available: Contact angle measurements of PAN and oPAN nanofibrous membranes; SEM images of oPAN nanofibers, CNF-MoSe 2 composites and pure MoSe 2 aggregates. See