Calcium bismuth niobate (CBN) ceramic, as a core element of high-temperature piezoelectric sensors, has attracted widespread attention due to its high Curie temperature within the class of Aurivillius compounds. However, CBN usually faces two shortcomings: poor piezoelectric constant and low resistivity. In this work, CBN-based ceramics with donor–acceptor ions (W/Co) co-substituted at B-site were prepared by solid-state reaction method, and structure–property relationship of ceramics was studied in detail. Co-substitution of W/Co ions effectively improved the electrical property and hardness of CBN ceramics. CaBi₂Nb${}_{1.91}$(W${}_{2/3}$Co${}_{1/3}{)}_{0.09}$O₉ exhibits enhanced electrical and mechanical properties including high resistivity of $～10^7\mathrm{\Omega }?$cm at 500°C, piezoelectric constant of $～15.3$ pC/N and hardness value of $～3.57$$$GPa. These values are two orders of magnitude, over two times, and 1.36 times higher than those of pure CBN ceramic, respectively. This work provides a reference for exploring other bismuth-layered structural ceramics.