The hairy poly(methacrylic acid-co-divinylbenzene)-g-poly(N-isopropylacrylamide) (P(MAA-co-DVB)-g-PNIPAm) nanocapsules with pH-responsive P(MAA-co-DVB) inner shell and temperature-responsive PNIPAm brushes were prepared by combined distillation-precipitation copolymerization and surface thiol-ene click grafting reaction using 3-(trimethoxysilyl)propyl methacrylate-modified silica (SiO2-MPS) nanospheres as a sacrificial core material. The well-defined PNIPAm was synthesized by a reversible addition fragmentation chain transfer (RAFT) polymerization. The chain end was converted to a thiol by chemical reduction. The PNIPAm was integrated into the nanocapsules via thiol-ene click reaction. The surface thiol-ene click reaction conduced to tunable grafting density of PNIPAm brushes. The grafting densities decreased from 0.70 chains nm(-2) to 0.15 chains nm(-2) with increasing the molecular weight of grafted PNIPAm chains. Using water soluble doxorubicin hydrochloride (DOX center dot HCl) as a model molecular, the tunable shell permeability of the nanocapsule was investigated in detail. The permeability constant can be tuned by controlling the thickness of the P(MAA-co-DVB) inner shell, the grafting density of PNIPAm brushes, and the environmental pH and temperature. The tunable shell permeability of these nanocapsules results in the release of the loaded guest molecules with manipulable releasing kinetics. (C) 2014 Wiley Periodicals, Inc.