Recently, lithium-sulfur (Li-S) batteries have been greeted by a huge ovation owing to their very high theoretical specific capacity (1675 mAh·g −1) and theoretical energy density (2600 Wh·kg −1). However, the full commercialization of Li-S batteries is still hindered by dramatic capacity fading resulting from the notorious “shuttle effect” of polysulfides. Herein, we first describe the development of a facile, inexpensive, and high-producing strategy for the fabrication of N-, O-, and S-tri-doped porous carbon (NOSPC) via pyrolysis of natural wheat straw, followed by KOH activation. The as-obtained NOSPC shows characteristic features of a highly porous carbon frame, ultrahigh specific surface area (3101.8 m 2·g −1), large pore volume (1.92 cm 3·g −1), good electrical conductivity, and in situ nitrogen (1.36 at %), oxygen (7.43 at %), and sulfur (0.7 at %) tri-doping. The NOSPC is afterwards selected to fabricate the NOSPC-sulfur (NOSPC/S) composite for the Li-S batteries cathode material. The as-prepared NOSPC/S cathode delivers a large initial discharge capacity (1049.2 mAh·g −1 at 0.2 C), good cycling stability (retains a reversible capacity of 454.7 mAh·g −1 over 500 cycles at 1 C with a low capacity decay of 0.088% per cycle), and superior rate performance (619.2 mAh·g −1 at 2 C). The excellent electrochemical performance is mainly attributed to the synergistic effects of structural restriction and multidimensional chemical adsorptions for cooperatively repressing the polysulfides shuttle.