Hollow nanostructures are of great scientific and technological importance for extensive applications in photocatalysis, drug delivery, wastewater treatment, etc. In this study, we have developed a facile hydrothermal method for the large scale fabrication of alloyed ZnxCd1-xS double-shell (DS-ZnxCd1-xS) hollow nanospheres using hierarchically porous ZnS nanospheres as sacrificial templates and the reagent Cd(Ac)(2) as a Cd source. The growth mechanism of double-shell hollow nanospheres has been studied and illustrated by investigating the morphological evolution of the inter-mediated products. Moreover, the chemical composition and void space between the double-shells of the as-obtained alloyed ZnxCd1-xS hollow nanospheres can be regulated by adding a certain amount of Cd(Ac)(2). The optical properties and band structures have been investigated using UV-vis diffuse reflectance spectroscopy (DRS), Mott-Schottky analysis and valence-band (VB) X-ray photoelectron spectroscopy, respectively. When evaluated for their photocatalytic properties, the as-prepared alloyed Zn0.46Cd0.54S double-shell (DS-Zn0.46Cd0.54S) hollow nanospheres exhibit excellent hydrogen production, and a H-2 evolution speed of up to 4.11 mol h(-1) g(-1) is reached under irradiation of visible light (lambda > 420 nm).