Selective functionalization of mesoporous silica nanospheres (MSNs) is crucial for nanoengineering of MSNs.Herein, we have combined surface-protected etching strategy and cationic surfactant assisted etching strategy to prepare functionalized MSNs with extally attached amino groups. The extally attached NH2 groups endow the catalysts with excellent catalytic performance for nitroaldol reaction between nitromethane and benzaldehyde. In addition, those NH2-MSNs can also be used to support gold nanoparticles, which display very good catalytic performance for reduction of 4-nitrophenol. It can be envisioned that the synthesis protocol developed in this work could also be extended to nanoengineered MSNs, which provides opportunities for nanoreactors design.