Epoxy resin, as a thermosetting polymer material with good performance, has been limited in application due to its high flammability. In this investigation, porous CuO-ZnO hollow spheres (CZHS) were prepared by a hydrothermal method. By incorporation with ionic liquids loaded CuO-ZnO hollow spheres (CZHS@Ils) and ammonium polyphosphate (APP) into epoxy resin (EP) matrix, a new composite flame retardant material, named as EP/7.5APP/1.5CZHS@ILs, was developed for improvement of their thermal insulation and flame retardancy. The thermal conductivity of EP/7.5APP/1.5CZHS@ILs was measured to be 0.0197 W m(-1) K-1 , which is lesser than that of APP incorporated epoxy resin (EP/APP), demonstrating good thermal insulation capability. The flame retardancy were assessed using the limiting oxygen index (LOI) test, the Vertical flame testing (UL-94) test, and the cone calorimeter (CC) test. The results obtained from LOI test show that the EP/7.5APP/1.5CZHS@ILs has good flame retardancy with a LOI value of up to 28, better than that of pure EP which has a LOI value of 19.2. Moreover, a V-0 level of the EP/7.5APP/1.5CZHS@ILs was observed from the UL-94 test. The peak heat release rate (PHRR) was reduced to 257.9 kW m(-2) , which is 74.8 % lower than that of the pure EP. Such results are attributed to the synergy effect of CZHS@ILs and APP which offers the epoxy resin excellent flame retardancy. Taking advantages of the excellent thermal insulation, flame retardancy and better mechanical properties, the as resulted EP/7.5APP/1.5CZHS@ILs may hold great potential for future thermal insulation and flame-retardant applications of energy saving building.