As　an　effective　approach　toward　sustainability　and　global　carbon　balance,　the　reductive　conversion　of　CO2　into　value-added　chemicals　is　of　considerable　significance.　Here,　by　simply　calcining　the　mixture　of　NH4SCN　and　KCl　in　an　air　atmosphere,　potassium　dopants　and　negatively　charged　electron-rich　centers　are　simultaneously　introduced　into　carbon　nitride　materials　via　a　metalation　engineering　strategy.　The　resultant　metalized　catalysts　with　deprotonated　imide　sites　and　doped　potassium　ions　demonstrate　much-enhanced　activity　for　catalyzing　CO2　reductive　hydrosilylation　with　excellent　conversion　and　＞90%　selectivity,　whereas　the　pristine　carbon　nitride　catalyst　shows　only　negligible　activity.　Both　experimental　and　theoretical　results　reveal　the　crucial　role　of　the　negatively　charged　electron-rich　centers　and　potassium　dopants　in　tailoring　the　energy　band　positions　and　electronic　structure　for　the　efficient　donor-acceptor　interaction　and　much　increased　driving　force　for　CO2　reduction.　The　present　work　offers　molecular-level　insights　into　the　boosted　CO2　reduction　activity　via　engineering　the　electronic　structure　of　the　metalized　carbon　nitride　catalyst　and　reducing　the　energy　offset　between　frontier　molecular　orbitals　of　CO2　and　the　catalyst,　which　can　provide　a　conceptual　guide　for　further　development　of　efficient　catalytic　CO2　reduction　systems.　©　2022　American　Chemical　Society.　All　rights　reserved.