In recent years, various transition metal compounds have been extensively studied to deal with the problems of slow reaction kinetics and the shuttle effect of lithium-sulfur (Li-S) batteries. Nevertheless, their catalytic performance still needs to be further improved by enhancing intrinsic catalytic activity and enriching active sites. Doping is an effective means to boost the catalytic performance through adjusting the electron structure of the catalysts. Herein, the electron structure of CoSe 2 is adjusted by doping P, S with different p electron numbers and electronegativity. After S doping (S-CoSe 2 ), the content of Co 2+ increases, and charge is redistributed. Furthermore, more electrons are transferred between Li 2 S 4 /Li 2 S and S-CoSe 2 , and optimal Co-S bonds are formed between them with optimized d-p orbital hybridization, making the bonds of Li 2 S 4 /Li 2 S the longest and easy to break and decompose. Consequently, the Li-S batteries with the S-CoSe 2 -modified separator achieve improved rate performance and cycling performance, benefiting from the better bidirectional catalytic activity. This work will provide reference for the selection of the anion doping element to enhance the catalytic effect of transition metal compounds.