Electrospun carbon nanofibers (CNFs), with one-dimensional (1D) morphology, tunable size, mechanical flexibility, and functionalities by themselves and those that can be added onto them, have witnessed the intensive development and extensive applications in energy storage and conversion, such as supercapacitors, batteries, and fuel cells. However, conventional solid CNFs often suffer from a rather poor electrical conductivity and low specific surface area, compared with the graphene and carbon nanotube counterparts. A well-engineered porous structure in CNFs increases their surface areas and reactivity, but there is a delicate balance between the level and type of pores and mechanical robustness. In addition, CNFs by themselves often show unsatisfactory electrochemical performance in energy storage and conversion, where, to endow them with high and durable activity, one effective approach is to dope CNFs with certain heteroatoms. Up to now, various activation strategies have been proposed and some of them have demonstrated great success in addressing these key issues. In this review, we focus on the recent advances in the issue-oriented schemes for activating the electrospun CNFs in terms of enhancing the conductivity, modulating pore configuration, doping with heteroatoms, and reinforcing mechanical strength, in close reference to their applications in supercapacitors. The basic scientific principles involved in these activation processes and their effectiveness in boosting the electrochemical performance of CNFs are examined. Finally, some of the on-going challenges and future perspectives in engineering CNFs for better performance are highlighted.