Wastewater treatment is one of the fields of environmental science given special considerations due to water sanity. Various methods are used to treat wastewater. However, the utilization of nanotechnology has revolutionized wastewater treatment with remarkable efficiency. Electrospun nanofibers are considered as emerging and most promising material in wastewater purification due to their high surface area and exceptional properties. This paper reviews the application of electrospun nanofibers for wastewater treatment especially removal of toxic heavy metals from wastewater. An in-depth discussion on effects of the electrospinning process and fiber morphology on heavy metals’ adsorption have been summarized. Role of different polymer chemistries and that of materials incorporate in these polymers such as carbon nanotubes, graphene, different types of nanoparticles, and metal–organic frameworks for determining on metal adsorption has been discussed. Further, the impact of nanofibers’ modification and functionalization for the said purpose has been discussed.