Au@ZnO nanospheres with controlled core-shell and yolk-shell features were successfully fabricated through a facile template-based solvothermal method using carbonaceous layers as intermediate. The active carbonaceous layers containing numerous surface functional groups such as OH and C═O play key roles in fabrication of the Au@ZnO nanospheres. The structures of Au@ZnO can easily controlled by adjusting the concentration of Zn ions aqueous solution and/or the size of Au@C microspheres. The synthesis strategy proposed in this paper is also verified to be suitable for fabricating some other Au@metallic oxides nanospheres such as Au@SnO2 and Au@Fe2O3 with controlled structures. Furthermore, due to the synergic effect of the surface plasma resonance effect of Au cores and the large surface area of 122.67 m2 g-1, the Au@ZnO nanospheres with yolk-shell feature exhibite good photocatalytic activity and stability under visible-light irradiation.