This study evaluated a simple and useful route to the synthesis of mesoporous TiO 2 microcapsules with a hollow macro-core structure. A hydrophilic precursor sol containing the surfactants in the hydrophobic solvents was deposited on PMMA polymer surfaces modified by non-thermal plasma to produce mesoporous shells after calcination. The surface of the PMMA polymer spheres was coated with NH 4 F and CTAB to control the interfacial properties and promote the subsequent deposition of inorganic sols. These hollow type mesoporous TiO 2 microcapsules could be applied as an efficient substrate for the immobilization of DNA oligonucleotides.