The growing demand for nuclear energy and the promotion of nuclear technology applications will generate large quantities of cobalt-containing wastewater. The efficient removal of cobalt from radioactive wastewater is of great significance for the resource regeneration and environmental protection. However, conventional removal methods are constrained by the poor removal efficiency and slow removal kinetics. Herein, the sulfonated polyether ether ketone coated activated carbon fibers (anode)/activated carbon fibers (cathode) asymmetric electrodes was proposed to boost the Co(II) electrosorption performance. The experimental results showed that compared to traditional symmetric electrodes, the theoretical maximum electrosorption capacity (116.19 mg·g−1) had an exceptional enhancement of 69 %. The voltage and initial pH of the solution had an undeniable impact on the efficiency of cobalt electrosorption. Furthermore, more than 75 % of Co(II) was rapidly immobilized within 3 h. The kinetic fitting indicated that the electrosorption process was more appropriately described by pseudo-second-order kinetic model. The Co(II) removal efficiency was up to 80 % under the conditions of coexistence with Na+, Mn2+, Ni2+, Zn2+, Sr2+, and Cs+. More importantly, it combines two synthetic mechanisms of electrosorption and electrodeposition to realize the purification of cobalt-containing wastewater. Overall, considering the fast and highly-efficient cobalt removal performance and innate economy, the asymmetric electrosorption for cobalt removal provides new insights into the treatment of cobalt-containing wastewater.