Coating a second metal on the surface of ultrathin 2D nanosheets (NSs) could induce lattice strain and modify the electronic structure, thereby changing the surface reactivity. Herein, we report the effects of different crystal phases of Ru on the electrocatalytic performance of ultrathin Ru@Pt core-shell NSs for the methanol oxidation reaction (MOR). Importantly, Ru with a novel face-centered-cubic phase was found to have more effect on the electronic structure of Pt than Ru with a conventional hexagonal close-packed phase, thereby leading to improved electrocatalytic activity toward the MOR under acidic and basic conditions. It is believed that the strategy presented here would offer a new approach to the construction of bimetallic core-shell nanostructures with various promising applications.