S-scheme heterojunctions present excellent photocatalytic performance for water splitting. Herein, an ideal distinctive heterostructure of porous ZnO-CdS/Pt spherical-shell was achieved by template-free method. It possesses the H2-generated efficiency of 32.15 mM·h−1·g−1, significantly surpassing the single or binary compounds. The remarkable photocatalytic activity stems from the unique morphology, S-scheme mechanism and the coordination of noble metal. Exceptional porous spherical-shell structure can localize the light, promote light scattering, increase adsorption capacity and bring abundant active sites. The reduction in transfer distance for carriers, inhibition of electron-hole recombination, as well as diminution of mobility resistance endues the heterojunction with efficient carrier separation and strong redox capacity. The probable mechanism was also estimated by the characterizations of XPS, UV, PL, PEC, EIS, M-S and ESR. This article provides a new method for spherical-shell structure fabricated without template, and proposes a significant promise for the construction and application of highly efficient photocatalysts for H2-production.