MOF-derived carbon-based nanomaterials have attracted great attention due to the outstanding electrocatalytic performance, low-cost and super stability. To design an excellent catalyst, Fe, N and S codoped carbon matrix/carbon nanotube nanocomposites (Fe-N-S CNN) are prepared by pyrolysis of ZIF-8 impregnated with iron salt in this work. Benefiting from the synergistic effect of carbon matrix and nanotubes, abundant iron nitrides and thiophene-S active sites, the Fe-N-S CNN exhibits an excellent oxygen reduction reaction (ORR) performance with a half-wave potential of 0.91 V vs. RHE in alkaline conditions and 018 V vs. RHE in acidic conditions, while those of commercial Pt/C catalysts are 0.85 V vs. RHE and 0.795 V vs. RHE, respectively. Furthermore, Fe-N-S CNN as the cathode catalyst in a primary zinc-air battery shows a specific capacity of 700 mA h g(-1).