ZnO:LiAc nanopaticles were successfully synthesized though a colloidal-sol technique in nonaqueous solution under ultrasonic irradiation. The luminescent characteristics from blue to red can be tunable by varying [Li]/[Zn] ratios. The possible reason of tunable luminescent characteristics can be attributed to the increase of density of oxygen vacancies caused by Li+ adsorbed in the surface of magic-sized ZnO nanocrystals based on XRD, zeta potential and XPS results. What's more, it is found that SiO2 shell coated on ZnO:LiAc nanoparticles can improve the surface property of ZnO nanoparticles and enhance the PL emission intensity and optical stability. Due to its excellent luminescent characteristic and optical stability, as-prepared SiO2 coated ZnO:LiAc nanoparticles may be a promising candidate for some applications in high-efficiency low-voltage phosphor, solar cells and biological luminescent labels.