Investigation of optical properties of Ce3+-activated phosphors is not only of practical importance for various applications but also of fundamental importance for providing a basis to understand relevant properties of other lanthanide ions in the same host. We report herein a combined experimental and theoretical study of optical properties of Ce3+ in Li4SrCa(SiO4)(2). Photoluminescence properties of the material prepared by a solid-state reaction method are investigated with excitation energies in the vacuum-ultraviolet (VUV) to ultraviolet (UV) range at low temperatures. The band maxima in the excitation spectra are assigned with respect to 4f -> 5d transitions of Ce3+ at the Sr and Ca sites, from comparison between experimental and ab initio predicted transition energies. As a result of the two-site occupation, the material displays luminescence at 300-500 nm with a high thermal quenching temperature (>500 K), consistent with the calculated large gaps (similar to 1.40 eV) between the emitting 5d levels and the bottom of the host conduction band. On the basis of experimental and calculated results for Ce3+ in Li4SrCa(SiO4)(2), the energy-level diagram for the 4f ground states and the lowest 5d states of all trivalent and divalent lanthanide ions at the Sr and Ca sites of the same host is constructed and discussed in association with experimental findings.