A new white phosphorescent glass-ceramic Eu2+/Eu3+ doped SiO2-Al2O3-ZnO-K2CO3 is prepared by the melt quenching method and subsequent heat treatment. It′s X-ray diffraction (XRD) pattern,excitation spectrum and emission spectrum are measured and recorded at room temperature. By the X-ray diffraction diffusion (XRD) data,βZn2SiO4 is demonstrated to be the crystallites in the glass-ceramic. Based on the Scherrer equation,the average size about 35 nm of βZn2SiO4 nanocrystals is calculated. The intense blue emission band (400-460 nm) and red emissions (574,587,611,650 and 700 nm) assigned to 4f65d→4f7 transition of Eu2+ ion and 5D0→7FJ (J=0,1,2,3,4) transitions of Eu3+ ion respectively. They are simultaneously observed at room temperature under 372 nm excitation in the glass ceramics and the emission luminescence intensity increased significantly compared with the as-made glass. The results indicate that Eu2+/Eu3+ doped SiO2-Al2O3-ZnO-K2CO3 glass-ceramic can act as suitable materials for LED phosphors.