Uniform hollow, yolk–shell and double-shell Zn₂SnO₄/SnO₂ nanoparticles with cubic morphologies have been synthesized using “etching–second growth–annealed” methods. Due to the high light-harvesting efficiency and low recombination rate of the photo-generated electron–hole pair, double-shell structures of Zn₂SnO₄/SnO₂ nanoparticles show an obvious improvement in photocatalytic activity.