Process engineering and manufacturing technologies for structural control and multifunctionality in electrospun nanofibres

Electrospinning has evolved into a mature yet continually expanding technique for assembling fibrous architectures with dimensions spanning the micro – to nanometre range. Over the past two decades, process engineering and manufacturing technologies, ranging from solution formulation and field control to collector design, novel spinning modes, and integration with 4D printing have greatly extended its scope, enabling high precision in regulating fibre diameter, alignment, architecture, and ultimately multifunctionality. This work provides a coherent synthesis of these developments, tracing the interplay between materials chemistry, process physics, and structural outcomes. We examine established and emerging strategies for integrating electrospinning with additive manufacturing and data-driven process optimisation, thereby opening new avenues for multifunctional materials. Applications are considered across a spectrum that includes biomedical scaffolds, energy devices, environmental protection systems, and responsive textiles, with emphasis on how processing decisions shape structural and functional performance. Finally, we identify persistent bottlenecks in scalability, reproducibility, and sustainability, and outline prospective directions in which green chemistry, intelligent control systems, and hybrid manufacturing are expected to converge, positioning electrospun nanofibres – with enhanced structural control and multifunctionality – as a cornerstone of next-generation engineered materials.