Poly(arylene ether)s (PAEs) engineering plastics are a type of high-performance material which are excellent in thermal resistance, mechanical properties, and have low dielectric constant and anti-corrosion. Over recent decades, PAEs further combined with the electrospinning technology to fabricate as large surface-to-volume ratio and porosity membrane materials for high-performance applications. In this review, progresses of PAEs-based electrospun nanofibers and fiber reinforced composites including proton/anion exchange membranes, oil-water separation membranes, bio-scaffolds and humidity sensors, etc. are presented together with their corresponding high-performance applications in the fields of fuel cell, wastewater treatment, bioengineering and flexible durable sensor. Finally, current challenges and future development directions of PAEs electrospun nanofibers are discussed.