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. CaBi₂Nb1.91(W2/3Co1/3)0.09O₉ exhibits enhanced electrical and mechanical properties including high resistivity of ～107Ω?cm at 500°C, piezoelectric constant of ～15.3 pC/N and hardness value of ～3.57GPa. 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.