Silicate glass/Ni-NiO double shell composite hollow microspheres (DSCHMs) were prepared in large scale though a fast sol combustion route. Single shell silicate glass hollow microspheres (SGHMs) were used as low density support of the Ni-NiO composite shell, which also serve as the robust first shell of the DSCHMs. Ni-NiO composite shells were assembled on the surface of the SGHMs through fast combustion of a precursor mixture containing nickel ions, organic fuels in air. The thickness of the Ni-NiO composite shell can be tuned simply by controlling the repeating times of the Ni-NiO shell assembly. The electromagnetic property and microwave absorption performance of the as-obtained DSCHMs were investigated, which exhibit strong dependence on the thickness of the Ni-NiO composite shell. This work provides a new strategy for the high efficient fabrication of composite particles through fast assembly of functional shells with tailored composition, structure and electromagnetic properties on large scale. (C) 2017 Elsevier Ltd. All rights reserved.