This paper describes the preparation of PVdF/graphene oxide (GO) nanofiber composite membranes via electrospining and their removal characteristics of heavy metal ions (e.g., lead and cadmium). The synthesized GO and composite membranes were characterized by SEM, FTIR, Raman analysis, and tensometry. These results demonstrated the successful synthesis of GO with various functional groups and their incorporation into the PVdF nanofibers. In addition, the adsorption isotherm studies of the synthesized GO using both the Langmuir and Freundlich models were carried out. The PVdF/GO nanofiber composite membranes showed hydrophilic characteristics and higher pure water flux (up to 3 times) than that of a neat PVdF nanofiber membranes. The heavy removal rate of PVdF/GO20 increased gradually as a function of time which reached at 95.2% (Pb) and 98.3% (Cd) after 2 h, respectively. From these results, prepared PVdF/GO nanofiber composite membranes have shown a great potential to be utilized for the wastewater system.