Ribbon-like microfibers of a new composite of europium complex Eu(aspirin)3(Phen) (aspirin is acetylsalicylic acid; Phen represents 1,10-phenanthroline) and polystyrene (PS) were prepared successfully by electrospinning with different mass ratios of Eu(aspirin)3(Phen) complex to PS = 1:10, 1:40 and 1:160. The microfibers were characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and fluorescence spectrophotometry. It was found that the fibers displayed excellent photoluminescence properties compared with rare-earth complex. The photoluminescence intensity and the emission intensity of the peak at 616 nm (5D0→7F2) of Eu-ions increased with the Eu(aspirin)3(Phen) loading. No obvious fluorescence quenching was observed. Further discussion on the structural and optical properties of the microribbons was presented. This kind of materials might be expected to be applied for optical or optoelectronic devices.