In this report, different morphologies of poly(aryl ether)s (PAEs) fibers were prepared via an electrospinning method. It is interesting that the fibers with relatively large diameter possessed strong fluorescence intensity. Meanwhile, photoluminescence spectra indicated that the PAEs fibers exhibited the following luminescence characteristics (excitation wavelength (nm); color): 330-380, blue and 450-490, green. The color stability in solid state could be attributed to the chromophore and proper inter-chain aggregation. The water contact angle of fiber membrane was improved compared to that of flat film, it could reach to the 158 degrees. The hydrophobic and superhydrophobic of electrospun membrane were mainly caused by the rough surface. Moreover, these PAEs fibers also showed excellent thermal stability with glass-transition temperatures in the range of 251-298 degrees C, 10% weight loss temperatures in the range of 534-558 degrees C, and the weight residue more than 53% at 800 degrees C in nitrogen. This study extended a potential application in special textiles, optoelectronic sensors, and optical detectors. POLYM. ENG. SCI., 58:1945-1954, 2018. (c) 2017 Society of Plastics Engineers