A microwave-assisted heating method allows for the convenient and reproducible synthesis of defined Au–Rh core–shell metallic nanoparticles with tuneable shell thicknesses. Nanoparticles with shells as thin as two Rh monolayers can be prepared, which are effective in vapour-phase hydrogenation catalysis at room temperature without the need for pre-treatment. Particles with Rh shells consisting of two or four Rh overlayers show similar catalytic properties and are both significantly more highly active than pure Rh nanoparticles, per mol of Rh employed.