Removing Hg(II) from water is challenging due to the depletion and decrease of adsorption sites on adsorbents during the process. In this study, we have developed a fully scaffolded Ag/C adsorbent material through continuous optimization of the regeneration of adsorption site numbers during the adsorbent regeneration process. As expected, the Ag/C adsorbent exhibited a remarkable Hg(II) adsorption capacity, reaching up to 328 mg g–1. Furthermore, this adsorption capacity was maintained over 4 sorption–regeneration cycles owing to the persistent renewal of the inherent adsorption sites. The formation of the Ag–Hg amalgam was confirmed by XRD, HRTEM, and XPS, which were attributed to monolayer chemisorption. Moreover, a significant increase in the number of inherent adsorption sites on the Ag/C adsorbent was observed, which was attributed to the stretching of silver–mercury bonds during thermal regeneration. This resulted in the generation of a greater number of smaller Ag adsorption sites on the carbon supports. Additionally, DFT calculations confirmed that Ag/C adsorbent lowers Hg(II) adsorption energy and facilitates electron transfer, ensuring exceptional reusability in practical applications. Therefore, these findings offer a valuable approach for the advancement of Hg(II) adsorbents possessing superior efficiency and significant application potential.