The best performance of the phosphor Li(2)SrSiO(4): Eu(2+), Ce(3+) in terms of luminescence efficiency (LE), color rendering index (CRI) and color temperature (Tc) for light-emitting diode application was optimized with combinatorial approach. The combinatorial libraries were synthesized with solution-based method and the scale-up samples were synthesized with conventional solid-reaction method. Crystal structure was investigated by using the X-ray diffraction spectrometer. The emission spectra of each sample in combinatorial libraries were measured in situ by using a fiber optic spectrometer. Fluorescence spectrometers were used to record excitation and emission spectra of bulk samples. White light generation was tuned up by tailoring Eu(2+) and Ce(3+) concentrations in the single-phased host of Li(2)SrSiO(4) under near-ultraviolet excitation, but it exhibited low efficiency of luminescence and poor color rendering index. The effects of each level of the Eu(2+) and Ce(3+) concentrations on LE, CRI, and Tc were evaluated with the Taguchi method. The optimum levels of the interaction pairs between Eu(2+) and Ce(3+) concentration on LE, CRI, and Tc were [2, 1] (0.006 M, 0.003 M), [1, 2] (0.003 M, 0.006 M), and [3, 1] (0.009 M, 0.00 3M), respectively. The thermal stability of luminescence, the external quantum efficiency (QE), luminance, chromaticity coordinates, correlated color temperature, color purity including the composition ratio of RGB in white light, and color rendering index of the white light emission of phosphor were evaluated comprehensively from a bulk sample.