Electrospinning has emerged as a transformative technique for fabricating nanofibers (NFs), offering precise control over their morphology, composition, and functionality. This versatile process facilitates the production of fibers ranging from nanoscale to microscale with customized properties, integrating diverse materials and architectures for advanced research and industrial applications. This review presents recent advancements in electrospinning, addressing its fundamental principles, nanomaterial synthesis methods, and examples from a wide range of applications. The significant progress that are made in fabricating polymer, metal oxide, carbon, and composite NFs with diverse architectures such as porous, core-shell, hollow, and aligned structures is highlighted. Advanced electrospinning techniques, including coaxial electrospinning, aligned electrospinning, yarn electrospinning, and roll-to-roll processes, demonstrate the scalability and adaptability of electrospinning for the development of next-generation nanomaterials. Electrospun NFs are being actively applied to functional membranes, gas sensors, energy systems, and catalytic processes, addressing critical challenges in these respective areas. In conclusion, the groundbreaking potential of integrating artificial intelligence (AI)-driven optimization with sustainable material design, such as the use of environmentally-friendly "green" solvents, is emphasized. In the end, leveraging robotics-based electrospinning and AI-enhanced methodologies is essential to achieve stable scalability, optimized performance, and sustainability for research and industry.