Transition metal sulfides with designed nanostructures are expected to provide superior electrochemical performance when used as electrode materials for pseudocapacitors compared to their oxide counterparts. In this paper, hollow Co 3 S 4 dodecahedra were successfully prepared using cobalt‐based zeolite imidazolium skeleton (ZIF‐67) as the precursor and thioacetamide (TAA) as the sulfur source combined with a facile one‐step vulcanization process. The hollow cavity structure not only shortens the carrier transport distance but also provides a higher specific surface area and abundant active sites, which promotes an efficient mass transfer process. In addition, the one‐step synthesis of hollow Co 3 S 4 has greater advantages than the one‐step synthesis in terms of cost control and process simplification. The specific capacitance of the produced hollow Co 3 S 4 nanopolyhedra was 668 F/g at 1 A/g and remained at 353 F/g at 10 A/g when used as a pseudocapacitor electrode, demonstrating its superior multiplication capability. In addition, the capacitance retention is 86.4% after 5000 cycles at 4 A/g, indicating its long cycle stability. Notably, employing commercial activated carbon as negative electrode and the as‐prepared hollow Co 3 S 4 polyhedrons as positive electrode, the assembled asymmetry supercapacitor device delivers a high energy density of 20.7 Wh/kg at a power density of 716 kW/kg. The capacitance value of the device remains up to 81.4% after 2000 charging/discharging cycles. The simple synthesis process opens new opportunities to develop advanced hollow nanostructures exhibiting potential for various applications.

Cobalt‐based zeolitic imidazole framework derived hollow Co3S4 nanopolyhedrons for supercapacitors