Electrospinning is a technique employed to prepare nanofibers of polymer, ceramics, and composite that are used in the high electrostatic field. Alignment is an important step toward the exploitation and applications of these fibers. In the present report, super-long aligned luminescent composite Eu(DBM)(3)phen/PS fibers (DBM = dibenzoylmethane, phen = 1,10-phenanthroline, PS = polystyrene) were prepared via an electrospinning method. The key to the success of this method was the usage of high molecular weight PS (M-w = 4.4 x 10(5)) in the electrospinning solution and the low speed (>0.5 m/s) collecting drum. Luminescent properties of the composite fibers were systemically studied in comparison with that of the corresponding pure europium complex Eu(DBM)(3)phen. The results showed that the fluorescence lifetime of D-5(0) state and the luminescent intensity of Eu3+ in Eu(DBM)(3)phen/PS composite fibers increased gradually with the fiber diameter. The composite fibers with smaller diameter exhibited better photoluminescence stability than that of the pure complex Eu(DBM)(3)phen. (C) 2013 Elsevier Inc. All rights reserved.