Electrospinning, a common method for synthesizing 1D nanostructures, has contributed to developments in the electrical, electrochemical, biomedical, and environmental fields. Recently, a coaxial electrospinning process has been used to fabricate new nanostructures with advanced performance, but intricate and delicate process conditions hinder reproducibility and mass production. Herein, recent progress in new emerging parameters for successful coaxial electrospinning, and the various nanostructures and critical application areas resulting from these activities. Relationships between the new parameters and final product characteristics are described, new possibilities for nanostructures achievable via coaxial electrospinning are identified, and new research directions with a view to future applications are suggested. Coaxial electrospinning has contributed to developments in nanoscience including electrical, electrochemical, biomedical, and environmental fields. New emerging parameters are discussed that enable nanofibers with diverse nanostructures to be fabricated from a variety of materials. Additionally, critical application areas resulting from these activities are presented.