Abstract: The conversion of agricultural residual biomass into biochar as a sulfur host material for Li–S batteries is a promising approach to alleviate the greenhouse effect and realize waste resource reutilization. However, the large-scale application of pristine biochar is hindered by its low electrical conductivity and limited electrocatalytic sites. This paper addressed these challenges via the construction of Fe–N co-doped biochar (Fe–NOPC) through the copyrolysis of sesame seeds shell and ferric sodium ethylenediaminetetraacetic acid (NaFeEDTA). During the synthesis process, NaFeEDTA was used as an extra carbon resource to regulate the chemical environment of N doping, which resulted in the production of high contents of graphitic, pyridinic, and pyrrolic N and Fe–N_x bonds. When the resulting Fe–NOPC was used as a sulfur host, the pyridinic and pyrrolic N would adjust the surface electron structure of biochar to accelerate the electron/ion transport, and the electropositive graphitic N could be combined with sulfur-related species via electrostatic attraction. Fe–N_x could also promote the redox reaction of lithium polysulfides due to the strong Li–N and S–Fe bonds. Benefiting from these advantages, the resultant Fe–NOPC/S cathode with a sulfur loading of 3.8 mg·cm⁻² delivered an areal capacity of 4.45 mAh·cm⁻² at 0.1C and retained a capacity of 3.45 mAh·cm⁻² at 1C. Thus, this cathode material holds enormous potential for achieving energy-dense Li–S batteries.