Dandelion-like core–shell silica microspheres with hierarchical pores are synthesized by condensing a dissolved silica species on the surface of homologous nonporous silica particles in a microemulsion system formed by the complexes of N,N-dimethyldecylamine and hexadecyltrimethylammonium chloride. The microspheres have good monodispersity and center radial pores.