In this study, a facile and effective surface hydrophobic layer protected selective etching strategy has been adopted to fabricate organic functionalized hollow silica nanospheres (OHSNSs). Our experiments demonstrated that the morphology and structure of OHSNSs were greatly affected by the types of organosilanes and concentrations of cetyltrimethylammonium bromide (CTAB) as pore-making agent. At low concentration of CTAB (1.9 mg/mL(-1)), it was found that the protective effect of the hydrophobic layer of 3-thiocyanatopropyltriethoxysilane (TCPTES) was so strong that can be endured long time etching (8 h), leading to the formation of hollow core and organic porous shell structure. And yet, the protective effect of the hydrophobic layer of vinyltriethoxysilane (VTES) was too weak to withstand alkali etching, resulting in preferentially etched of the outer vinyl protection shell. Whereas, at a higher concentration of CTAB (2.5 mg/mL(-1)), for TCPTES, the irregular and capsules-like spheres were obtained. In contrast, for VTES, porous core/solid shell structures with shell thickness of 16 nm were generated. In addition, no particles were observed when the CTAB concentration was above 2.5 mg/mL(-1). (C) 2015 Elsevier B.V. All rights reserved.