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 Co3S4 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 Co3S4 has greater advantages than the one‐step synthesis in terms of cost control and process simplification. The specific capacitance of the produced hollow Co3S4 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 Co3S4 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.