Development of low-cost, high-efficiency, and environmentally benign adsorbents for mercury removal is of significant importance for environmental remediation. Herein, we report a novel porous puffed rice carbon (PRC) with co-implanted metal iron and sulfur, forming a high-quality PRC/Fe@S composite as a high-efficiency adsorbent for mercury removal from aqueous solution. The in situ-formed Fe nanoparticles in PRC are strongly coupled with sulfur via a supercritical CO2 fluid approach and dispersed homogeneously in the cross-linked hierarchical porous architecture. The pore formation mechanism of Fe on PRC is also proposed. The optimized PRC/Fe@S composite offers superior selective affinity, high removal efficiency, and ultrahigh adsorption capacity of up to 738.0 mg g-1. It is demonstrated that the hierarchical porous carbon in the PRC/Fe@S composite not only acts as a framework to stabilize and disperse Fe nanoparticles but also provides abundant pores and voids for absorbing Hg(II) from aqueous solution. More importantly, the absorbed Hg(II) can be reduced to Hg(0) by Fe and further chemically immobilized by sulfur. The enhanced coupled effect is discussed and proposed. Therefore, an innovative adsorption mechanism of adsorption-reduction-immobilization is proposed, which offers a new prospect in developing high-efficiency carbon-based adsorbents in environmental remediation.