Aiming at the problem that the matching between phosphors and chips has significantly influence on white LEDs, characterization and measurement of LED phosphors were presented. According to the measurement principle of phosphors, a double splitting system was presented. Phosphor’s spectral characteristics were analyzed, and three-dimensional spectral distribution was achieved by combination. Luminous efficacy, quantum efficiency and energy efficiency were brought forward to evaluate phosphor’s performance. By evaluating the matching between kinds of phosphors and LED chips with different peak wavelengths but the same power, the optimal matching was acquired. Results show that the system and evaluation method can not only determine LED phosphors’ characteristics, but also has significant meaning in the research of achieving high-efficiency white LEDs.