Submicrometer hollow microspheres with mesporous shells were prepared by a simple one-pot strategy. Colloidal silica particles were used as a particle stabilizer to emulsify the oil phase, which was composed of a polymerizable silicon monomer (TPM) and an inert organic solvent (PEA). The low interfacial tension between colloidal silica particles and TPM helped to form a Pickering emulsion with small droplet sizes. After the polymerization of TPM, the more hydrophobic PEA formed a liquid core, leading to a hollow structure after its removal by evaporation. BET results indicated that the shell of a hollow particle was mesoporous with a specific surface area over 400 m(2).g(-1). With PEA as the core and silica as the shell, each resultant hollow particle had a hydrophobic cavity and an amphiphilic surface, thus serving as a good colloidal collector for hydrophobic contaminants in water.