Mesoporous silica nanoparticles (MSNs) have emerged as one of the most promising vehicles for potential application in drug delivery. In this paper, we report a novel multifunctional nanocomposite composed of a magnetite nanocrystal core and a mesoporous silica shell (Fe3O4@mSiO2), end-capped with pH-stimuli-responsive hydroxyapatite (HAp) nanovalves for pH-responsive drug release. Iron oxide core and mesoporous silica shell nanoparticles were synthesized using a microemulsion method, and were then employed as templates for surface coating of hydroxyapatite. The efficient coating of the natural nontoxic component hydroxyapatite was achieved through a biomimetic mineralization process. The pH-responsive release of the model drug ibuprofen showed that the Fe3O4@mSiO2@HAp nanoparticles possessed pH-responsive drug-release functionalities. The dissolution of hydroxyapatite in an acidic environment triggers the release of the loaded drugs in Fe3O4@mSiO2@HAp nanoparticles.