As a widespread application of high power phosphor-converted white light emitting diodes (pc-WLEDs) with long lifetime and color-consistence, the highly reliable phosphor/silicone composite, one of core materials used for light-conversion, working under severe operation conditions has become increasingly necessary. This paper selects three widely used monochromatic phosphors (Aluminates, Silicates and Nitrides based) as well as a pristine silicone to determine the potential interaction effects in their phosphor/silicone composites operated under different environments. Firstly, the transient thermal quenching and long-term high temperature ageing tests are used to investigate the thermal stabilities of both monochromatic phosphor powders and phosphor/silicone composites. Furthermore, the degradation mechanisms of phosphor/silicone composites aged under the high temperature & blue light exposure and high temperature & high humidity conditions are studied by considering the interaction effect. The results show that: (1) the thermal stabilities of different phosphors are different and the phosphor/silicone composites have more severe thermal quenching effects than those of their corresponding phosphor powders, but with the similar degradation trends; (2) the blue light irradiation can deteriorate silicone which is related to the photolysis effect; (3) the moisture can accelerate the degradation of phosphor/silicone composites because the change of pH condition, owing to the dissolution of phosphor powders in moisture, can degrade both phosphors and silicone.@en