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ABSTRACT: We reported a novel method to fabricate hollow silica microspheres using nonionic surfactant nonyl phenol ethoxylated decylether (NP-10) micelles as template, n-octadecane as core and sodium silicate as silica precursor. The core materials were removed by ethanol during the reaction. Hollow structure formed without calcinations or chemical etching. Hierarchical silica hollow microspheres were prepared by changing the concentration of the reactants and reaction time. Size of the core materials was obtained from the temperature-dependent dynamic light scattering (DLS) measurement. Scanning election microscopy (SEM) and transmission electron microscopy (TEM) results revealed that ordered microporous hollow silica microspheres with thickness of shell about 200 nm and mean diameter 2.5 μm were prepared. Porosity and pore size were analyzed by Brunauer–Emmett–Teller (BET).Graphical abstractResearch highlights▶ Nonionic surfactant nonyl phenol ethoxylated decylether (NP-10) was used as template to fabricate silica hollow spheres. ▶ Size and morphologies of the hollow spheres could be tuned by changing the concentration of silica sodium or core materials. ▶ The core materials were removed by ethanol during the reaction. ▶ Neither calcinations process nor solvent etching was necessary to remove the core materials.