Designing oxygen reduction reaction (ORR) catalysts with excellent performance has far-reaching significance. In this work, a high-activity biomass free-metal carbon catalyst with N and S co-doped was successfully prepared by using the KOH activated awn stem powder as the precursor with organic matter pore-forming doping technology, which is named TAAS. The content of pyridine nitrogen groups accounts for up to 36% of the total nitrogen content, and a rich pore structure is formed on the surface and inside, which are considered as the potential active centers of ORR. The results show that the specific surface area of TAAS reaches 191.04 m2/g, which effectively increases the active sites of the catalyst, and the initial potential and half slope potential are as high as 0.90 and 0.76 V vs. RHE, respectively. This study provides a low-cost, environmentally friendly and feasible strategy for the conversion of low-value agricultural and forestry wastes into high value-added products to promote sustainable development of energy and the environment.