Nonwoven fiber mats composed of poly(phenylene ether) (PPE) and polystyrene (PS) blends were prepared by electrospinning of PPE/PS solutions in a mixture of chloroform and hexafluoroisopropanol. The blends showed higher electrospinnability and led to thinner fibers (200 nm-1.3 mu m) than the pure components, because of a proper balance of electrical conductivity and interaction with the electrospinning solvent. The charge retention of the electrospun fibers was evaluated and related to the blend composition and the electret properties of the components. It was found that the nonwoven mats were able to retain up to 60% of the initial surface potential after several days of annealing at temperatures as high as 140 degrees C, which is markedly higher than the charge retention of corona-charged compact films. The capability of the electrospinning technique, to inject charges into the bulk of the material and to orientate the dipoles of the PPE phase in the field direction at the same time, was related to the good surface potential stability of the PPE/PS electrospun fiber mats. The possibility of creating thin PPE/PS fibers with excellent charge retention capabilities makes these materials ideal candidates for electret filter and sensing applications. POLYM. ENG. SCI., 49:2430-2439, 2009. (C) 2009 Society of Plastics Engineers