The field of photo-responsive electrospun polymer nanofibers represents a significant advancement in materials science, providing innovative solutions across various domains, including sensory technologies, medical treatments, environmental monitoring, and smart devices. These nanofibers, characterized by their responsiveness to light, offer unique opportunities due to their high surface area, porosity, and ability to incorporate diverse functional materials. Electrospinning, a versatile technique that produces nanofibers with tunable properties, allows for the customization of these fibers' physical and chemical characteristics, making them ideal candidates for advanced applications. This review aims to provide a comprehensive overview of the development and applications of light-responsive polymer nanofibers. It discusses the techniques of integrating light-responsive functionalities into nanofibers, including chemical insertion and physical doping, and explores the diverse responses these nanofibers exhibit upon light exposure, such as photoisomerization, photochromism, photocatalysis, and alterations in wettability. The structure of the review includes an introduction to the fundamental principles of electrospinning and photo-responsiveness, followed by detailed sections on the various applications of these advanced materials. Finally, future research directions are suggested, focusing on the integration of multifunctional compounds and the exploration of advanced nanofiber morphologies to enhance the applicability and performance of these cutting-edge materials.