In this study, sulfur‐doped carbon nanotubes with germanium as a pre‐dopant (SGe‐CNTs) are successfully prepared by sequential doping of germanium and sulfur, and their activity oxygen reduction reaction (ORR) activity is evaluated. As comparison, Ge‐doped CNTs and S‐doped CNTs are synthesized. The electrochemical results reveal that both Ge‐doping and S‐doping could improve the ORR activity of CNTs. In the synthesis process of SGe‐CNTs, germanium is deemed to be an efficient auxiliary pre‐dopant, since germanium modifies the microstructure of CNTs, and germanium content on the surface of Ge‐CNTs decreases dramatically after sulfur doping. Meanwhile, sulfur content on the surface of SGe‐CNTs is much higher than that of S‐CNTs with equivalent sulfur‐comprising dopants. Due to the Ge pre‐doping effect and synergistic effect of S/Ge doping, SGe‐CNTs with appropriate ratio of Ge and S atoms exhibit prominently enhanced ORR performance compared with those of single Ge‐ or S‐doped CNTs. By virtue of the outstanding ORR performance, SGe‐CNTs materials are expected to be highly active and cost‐effective ORR electrocatalysts in metal‐air batteries and alkaline fuel cells. The excellent ORR catalytic performance of SGe‐CNTs could be ascribed to the auxiliary Ge pre‐doping effect.