It is an urgent task to develop highly efficient non-noble metal electrocatalysts in the direction of ORR,but still a huge and long-term challenge.Herein,an efficient one-step pyrolysis of Sichuan pepper powder,2,2-bipyridine,FeCl3,NaSCN,and ZnCl2 at 900 ℃ provides the FeS/ZnS@N,S-C-900 hybrid catalyst.Transmission electron microscopy (TEM) images and Mott-Schottky curves clearly reveal the in-situ constructed abundant FeS/ZnS-based p-n junctions dispersed on the biomass-derived porous carbon surface of FeS/ZnS@N,S-C-900.The as-prepared FeS/ZnS@N,S-C-900 hybrid exhibits superior ORR performance in comparison with Pt/C in 0.1 M KOH with high onset (Eonset) and half-wave potentials (E1/2) of 1.00 and 0.880 V vs.RHE,large limiting current density (JL) of 5.60 mA cm-2,and robust durability and methanol tolerance.Impressively,upon the light irradiation,FeS/ZnS@N,S-C-900 produces a photocurrent as high as ca.0.3 μA cm-2,resulting in further improvement overEonset,E1/2,and JL of FeS/ZnS@N,S-C-900 to 1.10 V vs.RHE,0.885 V vs.RHE,and 6.02 mA cm-2.Experiment in combination with theoretical calculations demonstrate the significant effect of FeS/ZnS heterojunction on the enhanced ORR catalytic activity of FeS/ZnS@N,S-C-900.This work is useful for the development of advanced heterojunction-based ORR catalysts for various energy conversion devices.