Luminescent polystyrene microspheres were easily fabricated from poly(styrene-co-methacrylic acid)and aqueous RE(III) chloride solution(RE=Eu, Tb) in the presence of 2,20-bipyridine as second ligand. The negative charges of carboxyl groups on the surface of microspheres coordinated with rare earth ions at first, such as complexes covalently linked to 2,20-bipyridine, resulting in strong photoluminescence. Various methods, including transmission electron microscope(TEM), scanning electron microscope(SEM), energy dispersive spectroscopy(EDS),Fourier transform infrared spectroscopy(FT-IR), and fluorescence spectrophotometer, were used to characterize the resultant polystyrene composite microspheres. This work highlights the idea that it is facile to synthesis luminescent microspheres by surface-modified method directly. Luminescent polystyrene microspheres were fabricated fabricated from poly (styrene-co-methacrylic acid) and aqueous RE (III) chloride solution (RE = Eu, Tb) in the presence of 2,20-bipyridine as second ligand. The negative charges of carboxyl groups on the surface of microspheres coordinated with rare earth ions at first, such as complexes covalently linked to 2,20-bipyridine, resulting in strong photoluminescence. Various methods, including transmission electron microscope (TEM), scanning electron microscope (SEM), energy dispersive spectroscopy (EDS), Fourier transform infrared spectroscopy (FT-IR), and fluorescence spectrophotometer, were used to characterize the resulting polystyrene composite microspheres. This work highlights the idea that it is facile to synthesize luminescent microspheres by surface-modified method directly.