In this paper, anticancer drug methotrexate (MTX) is applied as a coupling agent to fabricate Au@SiO₂ core–shell structures for the first time. Then, a novel kind of Au yolk/LDH shell nanoparticles is obtained by using Au@SiO₂ as the template. Finally, the in vitro cytotoxicity is examined and the result indicates that the yolk/shell nanovehicles loaded with MTX exhibit superior anticancer efficacy, compared to the free drug.