Efficient　photocatalytic　reduction　of　CO2　to　high-calorific-value　CH4,　an　ideal　target　product,　is　a　blueprint　for　C-1　industry　relevance　and　carbon　neutrality,　but　it　also　faces　great　challenges.　Herein,　we　demonstrate　unprecedented　hybrid　SiC　photocatalysts　modified　by　Fe-based　cocatalyst,　which　are　prepared　via　a　facile　impregnation-reduction　method,　featuring　an　optimized　local　electronic　structure.　It　exhibits　a　superior　photocatalytic　carbon-based　products　yield　of　30.0　mu　mol　g(-1)　h(-1)　and　achieves　a　record　CH4　selectivity　of　up　to　94.3%,　which　highlights　the　effectiveness　of　electron-rich　Fe　cocatalyst　for　boosting　photocatalytic　performance　and　selectivity.　Specifically,　the　synergistic　effects　of　directional　migration　of　photogenerated　electrons　and　strong　pi-back　bonding　on　low-valence　Fe　effectively　strengthen　the　adsorption　and　activation　of　reactants　and　intermediates　in　the　CO2　-＞　CH4　pathway.　This　study　inspires　an　effective　strategy　for　enhancing　the　multielectron　reduction　capacity　of　semiconductor　photocatalysts　with　low-cost　Fe　instead　of　noble　metals　as　cocatalysts.