The europium complex Eu(TTA)(3)(TPPO)(2) (TTA = thenoyltrifluoroacetone, TPPO = triphenylphosphine oxide) was incorporated into poly(methyl methacrylate) (PNIMA, M(w) approximate to 350 000), polystyrene (PS, M(w) approximate to 250 000), poly(vinyl pyrrolidone) (PVP, M(w) approximate to 1 300 000) matrixes and electrospun into various composite fibers. The thermal stability of these composite fibers is better than that of the pure europium complex. Their photoluminescence properties were studied in comparison to those of the pure complex. The results indicate that, in all of the composite fibers, the excitation bands of the ligands split into different components because of the distorted crystal field, which reduces the degree to which the (5)D(0)-(7)F(0) transition is parity-forbidden. In addition, the thermal stability of the photoluminescence of EU(3+) in the composite fibers is considerably improved over that of the pure complex. Also, the Eu(TTA)(3)(TPPO)(2)/PS composite fibers exhibit better photostability upon exposure to ultraviolet light. In the Eu(TTA)(3)(TPPO)(2)/PS composite, blue and green band emissions caused by fluorescent impurities appear and, together with the red emissions of EU(3+), produce white light, which might have a potential application in white light-emitting diodes (LEDs).