Photoluminescence electrospun fibers were prepared from poly(aryl ether)s solutions. The porosity and wrinkle fibers could be observed by scanning electron microscopy (SEM). The effect of solution properties on fiber surface morphologies was studied. Meanwhile, the rough fiber surfaces could make the electrospun membranes possess water repellency. The contact angles of electrospun membranes for water were around 140A degrees. The emission spectra of these membranes indicated that the fibers exhibited multi-color including sapphire blue, olive green and rose red. It could provide a proposal for improving flexible optoelectronic devices based on electrospun membranes of conjugated polymers.