A polypyrrole–cobalt sulfide composite counter electrode (CE) was prepared in this work. Firstly, polypyrrole (PPy) nanorods were prepared by an in situ polymerization method on FTO, then cobalt sulfide (CoS) nanoparticles were coated on PPy nanorods by the electrodeposition method. The DSSC with PPy–CoS CE exhibits superior photoelectric conversion efficiency than that based on platinum (Pt, one of common counter electrodes), which is 7.52%, improving more than 20% compared to Pt CE (6.19%). In addition, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) measurements demonstrated that the PPy–CoS CE exhibited excellent catalytic performance for I₃⁻/I⁻ solution.