A new Ca 2 La 8 (GeO 4 ) 6 O 2 (CLGO) compound has been synthesized via solid-state reaction process for the first time. The crystal structure of CLGO was refined and determined by Maud Program. The photoluminescence spectra (PL), cathodoluminescence spectra (CL), and lifetimes as well as temperature dependence of photoluminescence of CLGO:RE 3+ (RE 3+ =Eu 3+ , Tb 3+ , Dy 3+ , Sm 3+ , Tm 3+ ) were investigated in detail. Under the excitation of ultraviolet, CLGO:RE 3+ (RE 3+ =Eu 3+ , Tb 3+ , Dy 3+ , Sm 3+ , Tm 3+ ) show red, green, yellow, orange, violet emission, respectively.