The development of synthetic process for hollow silica materials is an issue of considerable topical interest. While a number of chemical routes are available and are extensively used, the diameter of hollow silica often large than 50 nm. Here, we report on a facial route to synthesis ultrafine hollow silica nanoparticles (the diameter of ca. 24 nm) with high surface area by using cetyltrimethylammmonium bromide (CTAB) and sodium bis(2-ethylhexyl) sulfosuccinate (AOT) as co-templates and subsequent annealing treatment. When the hollow magnetite nanoparticles were introduced into the reaction, the ultrafine magnetic hollow silica nanoparticles with the diameter of ca. 32 nm were obtained correspondingly. Transmission electron microscopy studies confirm that the nanoparticles are composed of amorphous silica and that the majority of them are hollow.