Rational fabrication and structure design of anode materials with high specific capacity and excellent cycling stability are of significant importance for the development of high-performance lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs). In this paper, a zeolitic imidazolate framework-8 (ZIF-8) with a unique polyhedral morphology and large size (about 2 μm) was successfully synthesized through a facile co-precipitation method. After successive carbonization and sulfidation, ZnS nanoparticles decorated on nitrogen-doped porous carbon polyhedra (ZnS/NPC) were obtained. When applied as the anode material for LIBs, the ZnS/NPC hybrid displays the highest reversible specific capacity for ZnS-based electrodes reported so far (1067.4 mA h g −1 at 0.1 A g −1 after 200 cycles), excellent rate capability (364.6 mA h g −1 at 4 A g −1 ), and robust long-term cycling performance (856.8 mA h g −1 at 1 A g −1 after 1000 cycles). As for SIBs, the resultant ZnS/NPC also exhibits a desirable capacity of 370.6 mA h g −1 after 100 cycles at 0.1 A g −1 and 289.2 mA h g −1 after 1000 cycles at 1 A g −1 . Such superior lithium and sodium storage performances should be attributed to the distinctive structure advantages inherited from ZIF-8, where the Zn ions were in situ converted to ZnS with high reactivity upon electrochemical cycling and the organic linkers were pyrolyzed to nitrogen-doped porous carbon polyhedra to enhance the conductivity of the hybrid and keep the structure stability during cycling.