Nanofibers have attracted extensive attention and been applied in various fields due to their high aspect ratio, high specific surface area, flexibility, structural abundance, etc. The electrospinning method is one of the most promising and effective ways to produce nanofibers. The electrospun nanofibers-based films and membranes have already been demonstrated to possess small pore sizes, larges specific surface area, and can be grafted with different functionalities to adapt to various purposes. The environmental applications of nanofibers are one of the essential application fields, and great achievements have been made in this field. To well summarize the development of nanofibers and their environmental applications, we review the nanofiber fabrication methods, advanced fiber structures, and their applications in the field of air filtration, heavy metal removal, and self-cleaning surface. We hope this review and summary can provide readers a comprehensive understanding of the structural design and environmental applications of electrospun nanofibers.