Eu2+ and Mn2+ co-doped Ca8Zn(SiO4)4Cl2 phosphors have been synthesized by a high temperature solid state reaction. Energy transfer from Eu2+ to Mn2+ is observed. The emission spectra of the phosphors show a green band at 505 nm of Eu2+ and a yellow band at 550 nm of Mn2+. The excitation spectra corresponding to 4f7-4f65d transition of Eu2+ cover the spectral range of 370–470 nm, well matching UV and/or blue LEDs. The shortening of fluorescent lifetimes of Eu2+ followed by simultaneous increase of fluorescent intensity of Mn2+ with increasing Mn2+ concentrations is studied based on energy transfer. Upon blue light excitation the present phosphor can emit intense green/yellow in comparison with other chlorosilicate phosphors such as Eu2+ and Mn2+ co-doped Ca8Mg(SiO4)4Cl2 and Ca3SiO4Cl2, demonstrating a potential application in phosphor converted white LEDs.