Hollow siloxane-based nanoparticles (HSNs) have attracted significant attention because of their promising unique properties for various applications. For advanced applications, especially in catalysis, drug delivery systems, and smart coatings, high dispersibility and monodispersity of HSNs with precisely controlled shell structures are important. In this study, we established a simple method for preparing colloidal HSNs with a uniform particle size below 50 nm by the reaction of colloidal silica nanoparticles with bridged organoalkoxysilane [1,2-bis(triethoxysilyl)ethylene: (EtO)(3)Si-C2H2 Si(OEt)(3), BTEE] in the presence of a cationic surfactant. Upon the formation of organosiloxane shells by hydrolysis and polycondensation of BTEE, the core silica nanoparticles were spontaneously dissolved, and a part of the silicate species was incorporated into the organosiloxane shells. The size of the colloidal silica nanoparticles, the amount of BTEE added, and the pH of the reaction mixture greatly affected the formation of HSNs. Importantly, colloidal HSNs having micropores and mesopores in the shells were successfully prepared using silica nanoparticles (20, 30, and 40 nm in diameter) at pH values of 9 and 11, respectively. These HSNs are potentially important for applications in drug delivery systems and catalysis.